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105-125°]. Slow isomerization of the 1,2-ax,eq-Re^(CO)g- (PR3)2 (R = Bun , Ph) complexes to diax-Reg(CO)g(PRg)g was observed in toluene solution t room temperature (half- life of 10 h (PPh3) or 1-2 days (PBu” )>. The l,2-eq,eq- R6g(C0)g(PRg)g complexes appear to be stable towards isomerization.(iij The Me3NO-assii3ted reaction of Reg(C0)^g and(PMegPh in WeCN (80°C) resulted in the formation of1.2-ax,eq-Re^(COJQ(PHe^Ph) (vide supra).(iii) The thermal reaction between ReglCO)^ and PR^(PR3 = PM@gPh ‘13 , PMePhg at elevated temperatures and for extended reaction times (eg. PMSgPh, 80-1000C, 60-96 h;161 PMePhg, ld0°C, 15 h ' yielded a product Identified as1.2-ax.eq-Be..(CO)„(PR-,)>■ (vide supra).(iv) The photochemical reaction between flegfCO)^ andPR3 (PRg = PMegPh, 161 PMePhg 1 ”') has also been reported toyield the 1,2-ax,eq-Re^(CO)g(PR^) ■ An analogous arsine derivative, 1.2-ax,eq-Re^(CO)g(AsMe^Ph) , has also been prepared by the photochemical reaction of R@g(C0)^Q with AsMegPh. '1 ‘
The first two cases can be explained in terms of replacement of equatorial ligand(s) from 1,2-eq,eq-Re.,(CO)Q- (L)g ((i) U ) 2 = n-olefin; (ii) L = NCMe), to give l12=eaie3-Re2(C0)8 (PR3)2> or l,2-ax,eq-Re,(C0)q(PR,)^, depending on the size of the phosphine ligand.
In the third case, formation of 1,2-ax,eq-Re^(CO) (PRg)g products in thermal reactions of Re? (C0)JO with PRg at elevated temperatures and extended reaction times, can be explained in terms of the initial formation of diax- Re2(C0)g("R3)2 (obtained from thermal reactions under less forcing conditions (shorter reaction times)166 and from the Pd-catalysed and Me^NO-assisted (solvent or CHCCg1’5)reactions of Re2(C0 )1Q with PRg), followed by metal-metal bond cleavage, and rearrangement and recombination to give the electronically favoured 1,2-ax,eq-Re..(CQ)q(PR^)^ isomer. The formation of 1,2-ax,eq-Re^(CO) (PRj)„ products photo- chemically (case (iv)), where Re-Re bond cleavage is likely, a is consistent with this proposal. Further, traces
of l.g-ax.eq-Re^COJjlPft;,^ isomer can be detected by IR spectroscopy in the cases of the reactions which give the diax-Re2(CO)g{PR3 )2 isomer (vide supra), suggesting that a small amount of isomerization to the 1.2-ax,eq-Ke^(C0)g(PRg)m isomer occurs even under milder reaction conditions. As described above, partial Isomerization of diax-Re„(C0)„- (PMe2Ph)2 to l,2-ax,eq-Re_(C0)a(P M e „ P h i n toluene solution (80*C, d h) has also been observed (u.-der normal laboratory light!. Thus a slow thermal isomerization of diax-Re^iCOJj- (PRg)g to 1,2-ax,eq-Re^tCO)Q(PRj)■■ can occur, provided the phosphine is not too large (vide infra).
Steric factors determine whether the 1,2-ax.eq- Re2(C0)a (PR3 )2 isomer is stable for a particular phosphine. Thus for PMegPh and PMePhg (Tolman cone angles'5 of 122= and 136° respectively), the 1,2-ax,eq-Re^tC0)„(PR^). isomers r.re obtained from the thermal reaction of Re2(C0)10 with PRg (case (ii)), but the thermal reaction between Re2(C0 )^Q and PPhg (Tolman cone angle15: ld5=) yields only diax- Re2(C0)a(PPh3)2 (140aC, 16 h ) . " 2 Further, no l,2~ax,eq- Re2(CO)g (PPh3>2 (as evidenced by sidebands in the IR spectrum of the diax-Re2(C0)6 (PPh3>2 product) is formed in the PdO- catalysed reaction of Re2(C0 )10 and PPh3 (vide supra).
Thus it would appear that the particular synthetic method employed, and the size of the phosphine ligand used, determine whether the dlax-, l,2-eq,eq- or 1,2-ax,eq-Re„(CO) (PR3 )2 isomer will be obtained. For a synthetic method predisposed towards the formation of equatorially substituted Re2(C0)g(Pn3J., isomers (cases (i)-(iv) above), l,2~eq,eq- Re2(C0)g(PR3)2 is obtained for small phosphines (Tolman cone angle range.- 105a-l21°), while large phosphines (Tolman cone angle range: 122‘,-1450) yield l,2-ax,eq-Re2(C0t»- (PR3)2 . For the larger phosphine ligands (Tolman cone angle range: 130‘,-ld5°), the l,2-ax,eq-Re2(C0)g(PR3). isomers are unstable, and slowly isomerize (rate increases with the size of the PR3 ligand) to d i e x - R e j C o y P R ^ .
ISO.2.1 Synthesis of Bej C O } ^ (n = 1,2) from thereaction of Re^tCO)^^ and PR . in the present.'., of Pd-catalysts
Re2 '10 ^ 63 n!gl 0,25 mmol) and 50 mg Pd-catalyst (Pd/C (10% Pa), Pd/CaC03 (10% Pd) or PdOj were stirred in xylene ilO m6), to which was added PR^ (0.75 mmol). The reaction solution was refluxed at ldO°C for 1 to 9 h, depending on t' osphine used (see Table 15.5). The progress of the inaction was monitored by TLC (Silica; eluent: ethylacetate: petroleum ether (60-100°C), 1 .• 3). The product(s) were isolated by preparative layer chromatography (Silica; eluent as for TLC), extracted with benzene, and cryau-illized from benzene-hexane solution, to yield colourless to yellow
ISO 2.2 Synthesis of ReJCO)^ (n = 1,2) hy the NMe^O-assisted reaction of R e JCO)^ with PR^ ..i CH^ce
Reg(CO)^Q (163 n.g, O.i'5 mmol) was dissolved in C"gCtg (10 me), to which PR^ (0.75 mmol) was added, followed bj NMegO'2HgO (SO mg, 0.54 mmol) t-.ssolved in degassed MeOH (5 mt). The reaction solution was heated at 40°C for 8 h.Che progress of the reart.on was monitored by TLC (Silica; eluent: ethylacetate: petroleum ether (80-100°C), 1:3). The products were isolated by preparative layer chromatography (Silica; eluent as for TLC), extracted with CHgCtg, and recrystallized from CHgCSg-pentane solution, to yield colourless to yellow solids.150.2.3 Preparation of an Isomer of Re^tCOI.^PMepPh),,
Rc2(C0)^q (653 mg, 1 mmol), was dissolved in aeetonitrili MeCN (10 m6), and the solution heated at 80»C. To this solution was added NMe.jCi'SH O (234 mg, 2.1 mmol) dissolved in degassed MeOH (10 me). Reaction was Instantaneous, as evidenced by the colour change of the reaction solution from colourless to pale yellow. Then PMe^Ph (2.1 mmol) was added to the reaction solution, and the mixture heated at 80°C for 2 n. The product was Isolated by column chromatography (2cm x 40cm column, silica; gradient elution with hexane-
benzene solutions, starting with hexane and ending with benzene). Recrystallization from CH2C52~pentane solution gave a cream solid.150.2.4 Preparation of an Isomer of Re (CO) (PMePh^
Re2(C0,'10 (667 mg, 1.02 mmol) and PMePhg (4.0 mmol) were refulxed in xylene (17 m<j at 136*C for 15 h. During this time the solution changed from colourless to an intense yellow. The xylene was removed on a rotary evaporator, and the yellow oily residue pumped under vacuum for several days to remove excess phosphine, to give a yellow solid.
15E. The Crystal and Molecular Structure of diaxlRe^COWPMe^Ph) -1
15E.1 Introduction
Although the crystal and molecular structures of three" Mn2(CC;lt,_n(PR3)ri (n & 1, compounds have beendetermined by X-ray crystallography, no analogous dirhenium carbonyl-phosphine complexes havo been studied crystalio- graphically.
From IR spectral data (see section 15B), the geometry of the majority of Re2(C0)g(PR3) and Re2(C0)g- (PR3)2 products is expected to be the same as that of The analogous Mn2(D0)g(PR3 ) and Mn2(C0)g(PR3)2 complexes, viz. axial and dlaxial phosphine substitution respectively.An X-ray cryatallographic study of the complex dla/(fte„- (CO)g(PMe2Ph)23, product of the PdO-catalysed reaction between Re2(C0)10 and PMegPh (see section 15D), was undertaken with a view to confirming this prediction.
Further, the structural investigation of dlax- iRK2{C0)8(PMe2Ph)23 was undertaken as part of an extension •f the chemical, mechanistic and structural studies of j3 nitrile derivatives of dirhenium decacarbonyl (see chs.'{I ttnd XIV) to other donor ligands. Specifically, the otvuytural effect (if any) of the bulkier phosphine ligand (Tt.lian cone angle61 for PMegPh: 122*; values from MO calculations'6*: 139.8* (staggered), 155.6* (eclipsed)) on the Re2(C0)g unit was of interest. For example, incrde&ed
m - :
eteric bulk could affect the phenomenon of the bending in of the equatorial carbonyl ligands towards the metal-metal bond, observed in the parent carbonyl, Re^CCC)^,111 and in a series of dirhenium decacarbonyl-isonitrilG derivatives,
Re2(C0)10-n(GNR)n tn = l~41 (see ch- XIV)'15E.2 Discussion of related Mn^CCOJ^^ (n = l,gj Structures
As has bevi. 'ntioned, no cryatallographic studies of Re2(C0),c_n(PRg)ri (n = 1-4) complexes have been reported. However, X-ray crystallography has been used to determine the structures of the related manganese complexes, ax- a y r o y P M e j P W , " ' d i a x - M n ^ C O y P M s P h . ) a n d diax- Mng(CO)g(PEt2 ) g . A l t h o u g h bond length values for the manganese complexes cannot be compared to those of [Re2(C0)g(PMe2Ph)».], overall molecular conformation is comparable, The salient structural features of the Mn2(CO)10_n(PR2)n (n = 1,2) complexes will thus be discussed.
Crystal data and selected bond parameters for the Mn2 (CO?10_n(Pfi3)n (n - i,2> structures are given in Table 15.8. In all tnree cases, the dimer adopts a staggered conformation, with C-Mn-Mn-C torsion angles close to the ideal 45°. For the mono-substituted Mn2fC0)g (PHe2Ph), the phosphine ligand occupies an axial position; for the bisphosphine complexes, Mn2(CO)g(PRg)2 (PR^ = PMePhg, PEt^), phosphine substitution is diaxial. The observation that phosphine ligands occupy axial sites, rather than electronically favoured equatorial positions, is rationlissed in terms of the steric requirements [Tolman cone angles”s: Pt-tegPh, 122"; PEtg, 132"; PMePhg, 136"] of the bulky phosphine ligands111 (see Section 15D; see also ch. XII for a discussion of electronic and nteric factors governing ligand site preference in Mg(CO) (M = Re,Mn) complexes).
Interestingly, an X-ray cryatallographic structure determination of Mn2(CO)g(AsMe>,:'h)2lss has shown that this molecule h'is an eclipsed conformation, with an arsine ligand occupying an equatorial site on each Mn-atom. This crucial difference is ascribed to the longer Mn-As bond distance (av. 2.46A, cf. av. Mn-P, 2.23%, for diax-Mn^COJg-
(PMePh2)2ls*) which reduces repulsion between substituent groups and the carbonyls, hence permitting the electronically favoured equatorial substitution. Steric strain in this molecule is however reflected in the marked angular distortions (eg. Mn-Mn-As: 103*, instead of the ideal 90c) caused by close contacts between the phenyl ring and twoi of the equatorial carbonyls on the other Mn-atom. The unusual eclipsed conformation is probably adopted in order to minimize repulsions betn-een the ersine substituents and the equatorial CO ligands, as repulsive interactions between the twci sets of carbonyl groups Is expected to be greater in the eclipsed tnan in the staggered conformation.1311
Significantly, for all the three (n = 1,2) structures, the Mn'-Mn-COeq bond angles are less than 90°, ie. the equatorial carbonyls bend in towards the Mn-Mn bond. The significance of this will b'- discussed in section 15E.3.4.
In all three structures, the Mn-C-0 bond angles are in the range 171 - 178°, as expected.11
15E.3 Discussion of the structure of diax[Re .(C0)Q{PPhMe^)„1 (Vr r)
The molecular structre of diax[Re2(CO)Q (PPhMeg)2 ( v n ), and the iiunbering system used in the crystal structure determinate"! , is shown in Fig. 15.5. The compound crystallizes in the monoclinic centrosymmtitric space group C2/6, with 2 - 4 . A view of th 1 unit cell, looking down the b-axis, io shown in Fig. 15.6. Bond lengths and bond angles are given in Tables 15.9 and 15.10 respectively. Average bond angle and b<...'! length data is summarized in Table 15.11. The molecule adopts a staggered conformation, with diaxial phosphine substitution. The main structural features will be discussed in detail.15E.3.1 Diaxial phosphine substitution
The two phosphine ligands occupy the axial positions, as expected fiom IR data (section 1QD). This ie in contrast to the structure of Reg(CO) (CNCgHgMeg-2,6)^ (see ch. XIV), where the two isonitrile ligands occupy electronically favoured equatorial sites. This is an example of the
similarly for the other atoms).
%of the taiit cell of diax-[Re^(CQ) 3 (PMe2Ph),j. ■ -il), looking down the
dominance of ateric factors over electronic site preference in the case of the bulky phospbine ligand. (For the Re2<CO)8<CNC6H3Me2~2,6)2 and Re2(C0)8(PPhMe2)2 structures, the bulky CgHgMeg-2,6 groups are much further removed from the Re atom than the PPhMSg groups viz. adding the av. bond lengths for the linear Re-CN (2.05%), C-N (1.15A) aqd N-'iR) (1.43A) tones gives an effective av. Re...C(R) distance of d.C3. , of. Re-P distance of 2.35%; the lesser steric bulk of the isonitrile ligand is also reflected in the "fan-shaped" angles"" for CXCgHgMeg-2,6 of 106* (wideness) and P3* (thickness)).
Axie-1 "tution has also been observed in relatedKn2(C0 (n = 1,2) structures (see section 152.2).The dV •! derivative, Mn2(C0)g(CNBu*)2 ("fan-shaped"angles"1' for vi.du*: 70* (wideness) and 68” (thickness)) is again equatorially substituted (see ch.XIV). Hence the size of the metfl atom seemingly has no effect on the substitution geometry.15E.3.2 The Re-Re< Re-P and Re-CO bond lengths
In diax[Re2 (C0)5(PMe2Ph)2] the Re-Re bond length is 3.044(1)A, only fractionally longer than that of 3.041(1)% in the parent carbonyl, Re2(C0)10.'Se The substitution of a carbonyl trans to the metal-metal bond by a poorer n-accepting1',a phosphine ligand, and the consequent increase in electron density on the metal atoms, perhaps in anti' bonding orbitals, might be expected to result in an increase in metal-metal bond length. Such effects have been observed for phosphine-substituted metal clusterseg. rsgfaw^fppiy,'" fiu3(C0)n (PPh^),!;e oe3 (co)u -[P(0Me)g],' (0s6(C0):L7[P(0Me)3]4),8 e and has also beenascribed to ligand packing effects,ie. congestion between phosphine and carbonyl groups causes expansion of the metal core.27 ’ Further, kinetic studios111 have shown that the Mn-Mn bond strength in Mn2(C0)8(PR.)-, is less than in
The av. Re-CO bond length is 1.94'(2)A, similar to that of 1.976(6)A for the av. Re-CO(trans to CO) bond length
TABLE 15.9 : Bond 1sngths (A) for diax[Re (CO) (PMe Ph) ](VII)
R(x,y,z)-Re(x,y,
Re-C(t)Re-C(2)Re-C(3)Re-C(4)c ( ; ) - o ( i )
C(2)-0(2)C(3)-0(3)C(4)-0(4)P-C(5)P-C(6)P-C(7)C(7)-C(8)C(8)-C(9)C(9)-C(10)C(10)-C(11)C(11)-C(12)C(12)-C(7)
i-z;)3.044(1) 2.349(5) 1.954(21) 1.949(21) 1.946(20) 1.921(21) f. 163(21) 1.201(24) 1.178(24) 3. 130(22) 1.836(28) 1.836(23) 1.826(22) 1.387(31) 1.434(33) 1.339(34) 1.411(36) 1.419(31) i.378(29)
TABLE 15.10 : Bond angles (') for diax[Re2(CO)g<PMe2Ph)2](VIZ)
Re-C(1)-0(1) 178,0(18)Re-C(2)-0(2) 177.6(19)Re-C(3)-0(3) 177.2(17)Re-C(4)-0(4) 177.1(18)P-Re-ReIa 177.2(5)P-Re-C(1) 93.7(6)P-Rs-C(2) 91.7(6)P-Re-C(3) 92.4(6)P-Re-C(4) 93.7(6)C(1)-Re-Re18 85.0(5)C(1)-Re-C(2) 90.5(8)C(1)-Re-C(3) 90.4(8)C(1)-Re-C(4) 172.3(8),C(2)-Re-Reia 90.7(5)G(2)-Re-C(3) 175.7(8)C(2)-RarC(4) 87.1(9)C(3)-Re-Re'a 85.2(5)C(3)-Re-C(4) 91.5(8)C(4)-Re-Re‘a 87.8(5)Re-P-C(5) 116.0(8)Re-P-C(6) 116.7(8)Re-P-C(7) 113.8(6)C(12)-C(7)-C(8) 120.7(22)G(7)-C(8)-C(9) 119.2(23)C(8)-C(9)-G(10) 121.9(28)C(9)-C(10)-C(11) 117.6(27)C(10)-C(11)-C(12) 122.3(24)C(11)-C(12)-C(7) 117.9(22)P-G(7)-C(8) 119.1(18)P-C(7)-C(12) 120.2(17)G(5)-P-C(6) 101.0(11)C(5)-P-C(7) 102.7(11)C(6)-P-C(7) 104.8(10)
a Re' is related to Re by a 2-fold axis, generating the equivalent position (% /,i~z)
TABLE 15.11 : Average bond length (A) e "‘d bond angle (e) datadi^[Re2(CO)g(PMe2Ph) 2) (V.I)
Re-Re 3.044(1)Re-P 2.349(5)Re-C 1.94(2)P-C 1 .83(2)Re-Re-P 177.2(5)Re-Re-C 87.2(5)P-Le-C 92.9(6)G-Re-C(cis) 89.9(8)Re-C-0 177.5(18)Re-P-C 115.5(8)C-P-C 102.8(11)
in Re2<CO)g(CNC6H3Me2-2,6)a (ch. XIV). The Re-P bond length is 2.349(5)1.15E.3.3 Molecular conformation
Although the two sets of eq-carbony.l groups are staggered with respect to each other, the C-Re-Re-C torsional angles (see Appendix C,(VII)) deviate an av. o^6.9° from the ideal 45° (see Fig. 15.7). This is probably due to the influence of crystal packing forces (see section 15E.3.6).
The conformation of the ax-(PMe2Ph) groups with respect to the eq-CO groups is interesting in that the phenyl rings of the axial phosphine groups each eclipses a carbonyl ligand (see Fig. 15.8), with torsional angle'(see Appendix C,(VII)) of 0.0 for C(1)~ReTPtC(7). This feature could be due to
(i) steric factors.- th- .Methyl groups are then in Staggered positions with respect to the eq CO's (see Fig. IS.S'b)), with the smallest OC-Re-P-CHg torsional angle being 2'7.7°. However, in diax-Mn2(C0)8 (PEtg)2,116 all three ethyl groups are staggered with respect to the eq CO ligands.(ii) electronic factors: possible interactions betweenthe tr-cloud of a phenyl ring and an eclipsed CO.(iii) crystal packing forces (see section 15E.3.6).
The phenyl rings align parallel to the plai..,, ofthe eq carbonyl groups, as necessitated by steric factors.The two phenyl rings deviate from co-planarity by 30.8°The phenyl rinps are slightly puckered (see Table 15.12).
The av. Re-P-C and C-P-C bond angles of 115.5(8)" and 102.8(11)° respectively, and the av. P-C b e d length of 1.83(2)°, are similar to those for the related Mn2(C0)^Q_^- (PB3 )n (n a 1,2) structures (see Table 15.B).155.3.4. P-Re-CO, OC-Re-CO and Ro-Re-CO bond angles
^he axP-Re-COeq bond angles are obtuse (av. 92.9(6)° the eqOC-Re-COeq bond angles close to 90° (av. 89.9lti)°, and the Re-Re-COeq bond angles acute (av. 87.2(5)°, le, the equatorial carbonyls bend in towards the Re-Re bond. This
Figure 15.7: Newman projection of diax[Re^(CO)^(PMe^Ph)^] lookingdown the ,Re-Re' bond (phosphine groups omitted for clarity), Torsional angles (°), C-Re-Re'-C, between C-atoms adjacent in projection shown.
cr C7
Figure 15.8: Newman projections of dlaxtR8„(C0)»(PMg„Ph)-'J ■ showingconformation of phosphine groups relative to eq carbonyl ligands8(a) Newman projection of dlax[Re2(G0)8(PMe2Ph)l,], looking down the P-Re-Re'-P1 axis.
Figure 15.8 (cc-rvtd)
122.7118.3
Figure 15.8: (b> Newman projection of ax[Re(CO)^P(Me^,Ph)]fragment4 looking down the P-Re bond.
s Selected OC-Re-P-C torsional angles C ) shown.
TABLE 15.12 Least squares planes for phenyl rings in diax[Re2(CO)8(rMe2Ph)2](VII)
(a) Phenyl ring on P (i.e. C(7) Co C(12)f
Atom deviation(A)PC (7)C(8) -0.036C(9) 0.011C(10) 0.' ,/C(11) -0.037C (12) 0.013
Equation of plane :; (9.7474)x -i- (-1 .9024)y + (14.1819)g =-0.
Phenyl ring on P 1 (i.e. C(7l1 to C(12)1
At0ln deviation(A)P ‘C(7) 1C(#)'C(9)'COO)'C O O *C(12) 1
^ Equation of plane ; (9.7334)x + {1.9013)y + (n.i88Q)g = :
' t
effect of the bending in of the equatorial CO ligands towards the metal-metal bond is observed for related Mn;3(C0)10_n(PR3)n <n = 1,2) complexes (section 15E.2), as
well as for a series of M2^C0^10-n^CNR ri ^ = Re' n = 1-4’M «= Mn, n = 2,4) complexes (ch. XIV) and the parent carbonyls, MgfCO)^ (M = Re,Mn).1!a Hence this phenomenon would appear so be an electronic effect, unaffected by steric considerations. Various explanations have been proposed (see ch. XII), and Elian and .Hoffmann * have predicted the effect on the basis of MO calculations.15E.3.5 f:e-C-0 bond angles
The Re-C-0 bond angles are in the range 177(2)° to 178(2)° (av. 177.5°). Slight deviations from linearity (ca. 5°) of M-C-0 ligands is expected.”
15E.3.6 Packing
The overall conformation adopted by the molecule could be governed largely by crystal packing forces. The molecules pack in a regular fashion (Fig. 15.6). A notable feature is the way in which the phenyl rings of different molecules line up in rows down the cell.
According to Johnson's21,6 model of close-packing of CO's for metal carbonyl complexes, packing forces are responsible for distortions from ideal geometry. Crystal packing forces could account for several observed distortions in the diax[Re^(CO)^(PMa_Ph) ] molecule:-(1) An av. 6.0° deviation from ideal 45° C-Re-Re-Ctorsional angle.(ii) The slight deviation of the P-Re-Re-P unit fromlinearity, as evidenced by the P-Re-Re bond angle of 177.2(5)°
(iii) The deviation of the phenyl rings from co-planarity,jangle between mean planes of the two phenyl rings; 30.8°).(iv) The deviation from parallel alignment of the phenylrings with the planes of the C-atoms of the eq carbonyl groups. (Angles between mean planes: Ph(C(7) to C(12)) andeq C-atoms (0(1) toC((4)): 21.3°} Ph(C(7)' toC(12)),and eq C-atoms (C(1)'to 0(4)': 21.3°).
Other structural features that could be largely determined by crystal packing forces are the orientation of the PMegPh groups with respect to the eq CD's such that the phenyl rings eclipse an eq carbonyl, and the position of the phenyl groups relative to each other (ie. which CO ligard is eclipsed by the Ph rings). The role of crystal packing forces in determining overall molecular conformation should not be neglected.
15E.4 Experimental15E.4.1 Data collection
The compound diax[Re^(CO)g(PMe^Ph)^] was synthesized in the PdO-catalysed reaction between Re2(CO)10 and PMSgPh (section 15D). Recrystallization from diethylether-pentane solution under nitrogen at 20°C yielded fine colourless needlelike crystals.
Preliminary investigation by standard Weissenberg photography established the space group as the centred monoclmic C2/c, or the non-centrosymmetric Cc, from the absences hk<, h + k = 2n, hOf, 5 = 2n (h = 2n> and OkO, k = 2n. Refined cell constants were obtained during data collection on a Philips . PW1100 four-circle diffrat eter, using graphite-monochromated MoKo radiation (a = 0.71078) at room temperature {20°C). Lorentz and polarization
corrections were applied, and the data were empirically corrected for .. bsorption effects using the program DIFABS, written by N. Walker and D. Stua"t,$$’a and adapted by G. Kruger. ^ Crystal data end details of the structure analysis are summarized in Table 15,13.15E.4.2 Structure solution and refinement
Structure analysis and refinement were carried out using the program SHELX82. 8 Initial co-ordinates for the rhenium atoms were derived from a Patterson synthesis, and the positions of the other non-hydrogen atoms were found by difference Fourier syntheses. The structure was refined in the cenerosymmedric space group C2/a (No. !5).* The two halves of the molecule being related by a crystallographic2-fold axis. Positional parameters for all atoms,
and anisotropic temperature factors for the r^anium and phosphorous atoms, were refined by full-matrix least-squares analyses. In the initial stages, the phenyl rings were treated as rigid hexagons, but all restraints were removed in the later stages of refinement. Least-squares refinement was considered completed vAien all parameter shifts were less than 0.5%. At thin sf.^e the R-vai je waa 0,0602, Unit Waightr were used. Scattering factors for Re(0) were takexi from "Internscional Tables for X-tay Crystallography",461’ and anomalous dispersion corrections"6 for rhenium were made.
Final atomic co-ordinates for all atoms, and isotropic temperature factors of the cirbon and oxygen atoms are given in Table 15.14, and Table 15.15 gives the anisotropic temperature factors of the rhenium and phosphorous atoms. A listing of the Structure Factors is to he found in Appendix D.
The structure was also refined in the non-centrosymmetric space group, Cc (No. 9), and Hamilton's Statistical Significance Test on Uhu Crystallographic R Factor28 5 applied. At che 0.005 significance level, it was found that the hypothesis that the space group is C2/c and not Cc, could not be rejected.
TABLE 15.13: Crystal data and details of structure analysis fordlax[Re„(CO)fl(PMepPh).](Vll)
Formula
Crystal dimensions (miSpace groupa(A)MA)c(%)6(6)U(A3 )
0.19 x 0.09 x C C2/C (No. 15) 22.779(9,1 7.166(3) 17.249(7)
2804.33
F(000)Dc (gem-3)
X(A)Scan mode Range (°)Seen width (»)Scan apeod (•sec""1)Range of hki Measured intensities Unique reflections Internal consistency R-index Omitted reflections Cut-off criterion
MoKo (0.7107)
+11, +k,+<
Tdbla 15.14 : Final atomic co-ordinates, and isotropic temperature factorsfor the C and 0 atoms , of diax-fRe., (CO)p (PMe^Ph),,] (VII)
Atom x/a y/b c/z U(A2)
-0.0480(1) 0.1879(1) 0.1827(1) - ,-0.1249(2) 0.1968(8) 0.0824(3) -
0(1) -0.1253(6) 0.0013(20) 0.3011(8) 0.060(4)0(2) -0.0078(7) -0.2067(24) 0.1269(9) 0.078(5)0(3) 0 9174(8) 0.5811(25) 0.2423(9) 0.085(5)0(4) 0.C 2(7) 0.3659(24) 0.0789(9) 0.082(5)C(I) -0.0963(9) 0.0679(29) 0.2563(11) 0.051(5)0(2) -0.0218(9) -0.0551(30) 0.1486(11) 0.054(5)0(3) -0.0685(9) 0.4325(28) 0.2215(10) 0.051(5)0(4) 0.0085(9) 0.2956(30) 0.1194(11) 0.053(5)0(5) -0.1479(12) 0.4299(39) 0.0475(14) 0.082(7)0(6) -0.1112(10) 0.0815(34) -0.0093(13) 0.071(6)C(7) -0.1937(9) 0.0952(30) 0.1093(11) 0.054(5)0(8) -0.2067(11) -0.0889(35) 0.0896(13) 0.072(6)0(9) -0.2580(12) -0.1741(41) 0.1166(15) 0.089(8)0(10) -0.2959(12) -0.0782(41) 0.1564(15) 0.085(8)0(11) -0.2843(11) 0.1131(36) 0.1697(13) 0.074(7)0(12) -0.2320(10) 0.2001(33) 0.1490(12) 0.062(6)
Anisotropic temperature factors (A.) : of diax.[Re2(CO)8(FMe2Fh)2] (VII)
. the Re and P atoms
0.0412(6)0.048(4)
0.0422(5)0.063(3)
0.0419(4)0.040(3)
0.0019(4)0.005(3)
0.0043(3)0.001(2)
0.004(4)0.004(3)
X.-,.
Conc3 slon
The synthetic utility of catalysts such as PdO (alone or in combination with [ (r)-CgM^)Fe(C0)2]2 ) to bring about the substitution of GO by RNC ligands in transition metal carbonyl complexes under mild thermal conditions has been demonstrated for a wide variety of metal carbonyl complexes, including (Arene)Cr(CO)? , (CgHg)Mn(CO)g and Re^CO)^ . This catalytic synthetic rcte provided access to novel isonitrile- substituted derivatives of these carbonyl complexes, thus making the derivatives available for further chemical and structural studies.
X-ray crystallographic studies of representative isonitrile-substi tuted metal carbonyl derivatives were undertaken to establish the stereochemistry of the products. From an analysis of the bond data from these studies, together with a comparison of the structure to that of the unsubstituted parent carbonyl complex, the structural effect of ligand substitution was evaluated. Trends were rationalized in terms of electronic effects, and deviations explained by the influence of steric factors and/or crystal packing forces. Further, with the backing of the crystallographic studies, the relationship between molecular structure and IR spectral data was examined.
The crystal and molecular structures of (rnCgHgCOgMe)- Cr(CO)2(CNBu6) and ( )Mr...COl^lCNBu6) were undertaken largely in order to establish whether the anomalous IR spectra of these complexes could be explained in terms of molecular structure. No definite conclusion could be reached in this regard, but possible explanations for the anomalous IR data were advanced. If the effect is due to the bent C-N-C bond, crystal structure determinations of similar complexes which do nr' 'uy the anomalous IRspectral behaviour, eg. ' . Cr(CNCgHgMeg-2,6)(attempts to solve this 81 ,re unsuccessful),(n-CgHg)Mn(CO)g(CNCgHgMeg-2,v -y help clarify the issue, as such complexes would thus be expected to have a linear C-N-C bond. No explanation of the anomalous IR spectra of
the Fe(CO)g(CNR)q complexes could be found from the crystal and molecular structure of Fe(CO)3 (CNMe)g. The reason for the anomalous IR data is unclear.
A systematic study (spectral, structural and mechanistic) was conducted of the Reg(CO)^g_^(CNR)^ (n = 1-4) complexes. From an X-ray crystallographic study of a series of representative derivatives, viz. Reg(CO)g(CNBu^), RegfCOlg- (CNC6H3Me2-2,6)2, Re2(C0>7 (CNMe)3 and Re2<C0)6(CNC6H3Me2-2,6)d, it was shown that the increasing degree of isonitrile substitution has little structural effect on the dimer, relative to the parent carbonyl, Re2(C0)lo- In particular, the equatorial ligands (both CO and CNR) bend in towards the rhenium-rhenium bond, as in Re2(CO)10, despite the increased steric bulk of the isonitrile ligands. Further, the poorer -accepting RNC ligands do not result in an increase in the Re-Re bond length for the fle2 (CO)10 ^(CNR)^(n = 1-3) complexes, although a slight lengthening is observed for Re2(CO)g(CNC6H3Me2-2,6}d. A shortening of the Re-CO bonds trans to an RNC is however a general trend.The structures oi two manganese analogues, Mn2(CO)g(CNBu*)2 and Mn2(C0)j.(CNCgH3Me2-2,6)d , were also determined cryatallographically. The abr/e features are applicable, but here a lengthenim if the Mn-Mn bond relative to that in Mn2(C0)10 is observe)
It was found that . Ufferences in the IR and NMR spectra of the Re2(C0)g(CNR)^ and Mn2(C0)g(CNR)2 derivatives could be explained in terms of differences in the substitution geometry, is demonstrated by the crystal structure determinations of l,2-dleq-Re„(CO)g (CNCgH3Me2-2,6)2 and l,l-cl8-dieq-Mn2(C0)„(CNBut')2 , Kinetic studies on M2(CCi)io__n(CNBut)n (M a Mn, Re; n = 1-3) are in progress,,s and should provide information on the formation of isomers and the reaction pathways.
An X-ray crystal structure determination confirmed the diax-subsfcitution of Re2(CO)g(PMSgPh)g, obtained from the PdO-catalysed reaction of Re2(C0)^g and PMSgPh.However, an ax-eq i: >mer was prepared by alternate methods.
The substitution geometry of the latter isomer was established by IR spectral methods.
From a consideration of IR spectral data of Mg(C0)g(L)g (M = Re.Mn) complexes, backed up by X-ray crystallographic structural information, it was found to be possible to establish a correlation between IR spectral data (number of v(C0) bands, and intensity pattern) and molecular geometry.This has been done for all known isomers of Mg(CO)g(L)g, viz. 1,2-diex, l,2-RX,eq, 1,2-eq.eq, l,l-ax,eq and 1,1-cis- dieq. A synthetic challenge would be to tailor-make the missing isomer, 1,l-trans-dieq-M^CO)^L)2> to complete the
This work demonstrated that the catalytic synthetic route opens up new areas of metal carbonyl-isonitrile chemistry. Extensions of this method to other complexes can be invisaged, for exa ;hs full potential of the reactionbetween (n-CgHg)V . RNC in the presence of Pd-catalyst,is being further explored,iM
The approach of investigating substitution geometry and and structural effects of increasing ligand substitution, exemplified by the Ren(CO)10_n(CNR)n (n = 1-d) study, could be •'xMnded to other systems. Specifically, the Reg(CO)^_^- (P' ^ system could be further investigated. With stz tural data from X-ray studies of isomers of Re2(CO)7(PR3)3,together with IR spectra, a correlation could be established between IR data and substitution geometry, as has been demonstrated for the Mg(C0)g(Lcase.
In this work, monomeric an ' dimeric metal carbonyl complexes were studied. A lof extension would be to trimeric complexes, Trimers , ,<-i be of two types, viz. triangular (closed) eg. OSg(CO), ' r-r oper, linear eg. [Mn3(C0)14]"",217 or bent eg. ~ln(C0)^4]. Few systematic investigations have be< ' .„?rted on this latter class of compounds. Structural s'v : ; on these higher clusters along the lines of the Re^lv J^/RNC structural study would be expected to provide valuable information regarding the substitution geometry, molecular conformation and structural trends.
Appendix A
The Sources of Chemicals used In this study
All materials were used as obtained from the manufacturers,without further purification
(A ) General Chemicals(a) Strerc Chemicals Incorporated: RegtCO)^, ((CgHgJFefCOgjg,
:C6H6 )Cr(C0)3, (CgtigM«)Ci'(CO)3, (C^)Mn(CO)g, (C^)V(CO)^,Cr(CO)g, Fe(C0)g, PMe^Ph, PMePhg, PMe^. P 1CH2C6H5)' AeMe2phl
(b) Fluka *.0: tBuNC, E.G-MegC^NC, CgH^^NC, NMegO-2HgO.
(c) Merck Chemicals: PPh^, LlhCH^.
(d) British Drug Houses. Ltd. : PlOMe)^. CaCO^. CgHgCO^Me.
(e) Aldrich Chemical Co. Ltd.; CgHgCHgNC.
(f) Schuch: CtCOgMe
(B) Catalysts Supported metals, metals and metal oxides.(a) Strem Chemicals Incorporated; Re/C{5% Re), Dd/BaC03(5% Pd),
Pd/BaS04<5% Pd), Pd/A*gO^(5» Pd), Pt/A(gOg(5%Pt).
(b) Engelhard: Pd/C(5% Pd), Pt/C(5% Pt), Rh/C(5% Rh), Ru/C(5% Ru).
(c) Merck Chemicals; Pd/CaC03(10% Pd), Pd/C(10% Pd), Pt/C(10% Pt).
(d) Johnson Matthey Chemicals Ltd.: PdO, PtO,, Pd(metal).
(e) Analar: Zn(metal).
(f) Pierce Chemical Co. Ltd.: Pd-lmpregnated polymer (40 mesh).
(g) In addition, Activated Carbon, "Bergswerksverband", GmbH Type PK231, was a gift from Dr. G.J. McDougai.
(C) Other Sources(a) The following compounds were gifts from Dr. M,0. Albers:
t(C5Me5)Fe(C0)2]? ,i> [{C^Hg)Fe(CNCgH^Meg-Z,6)^]g,»' (C6H5Ct)Cr{CO)3, fla CoCe2.2H20, “•= MeNC,"' and the Pe(C0)3- (CNMe)2 "'2 used in the X-ray structure analysis.
Appendix A (contd)
(b) The following compounds were gifts from Dr. N.J. Coville:The samples of Mn2 (C0)a(CNBnt)2 and Mn2(C0)6(CNOgHgMeg-a,6>d used in the X-ray structure analyses, and the isotopically labelled Re2(13C0)1(). »"
(c) The sample of ax-Mn2(CO)g(PMSgPh} used for recording the1R spectrum (Fig, l l . r ( b ) ) was n gift from Or. E. Singleton.
Appendix B
General Experimental Details
(a) Synthetic Methods
All reactions wore routinely carried out under an inert atmosphere of argon in an appropriate round-bottomed flask. Oil baths (pre-set to the appropriate temperature) were used for the heating of the reaction solution. Generally, all solvents were deoxygenated prior to une by a rapid stream of nitrogen passed through the solvent.
Column chromatography was carried out using silica gel (Merck, "Kieselgel 60", 60-200um). Thin layer chromatography (TLC) was carried out on sill' a gel (Merck, silica gel 60 F-254), and preparative layer chromatography was performed using silica gel plates (Merck, silica gel 60 F-254, 20 x 20cm, layer thickness
Operations such as filtration, chromatography and routine recrystallizations, were generally carried out in air, unless otherwise stated.
For the purposes of obtaining crystals suitable for X-ray analysis, slow recrystallizetions were carried out either under nitrogen in a suitable solvent system at room temperature, of in a deoxygenated solution at -5°C.(b) Solvents
The following solvents were distilled under an atmosphere of nitrogen, prior to use:(!) benzene and tetvahydrofuran (THF), from sodium beiizophenonc
(11) toluene and xylene, from sodium(iii) hexane, heptane and dichloromethane, from calcium hydride(iv) pentane, from sodium benzophenone kefcyl, with diglyme
(diethylene glycol dimethyl ether).(c) Instrumentation
Infra red spectra wore recorded using either a Pye Unicam SP300 or a Jasco IRA 1 instrument. The 1R spectra of the Re2(C0)10 - (CNR) (n = 1-4) derivatives were recorded on a Pye Unicam SP300
Appendix B (contd)
spectrophotometer, at XS expansion.FTIR spectra were run on a Bruker IFS 85 FTIR spectro
photometer.All 1H NMR spectra were recorded using a Bruker WP30
FTNMR spectrometer. Spectra were run in C^Dg, relative to IMS (tetramethylsilane).
ss spectra were all obtained using a Varian MAT CHS spectrometer (operating at 70eV).
Melting points were determined using a Kofler micro-hotstage apparatus, and are all uncorrected.
Microanalyses were all performed by the MicroanaZyticaJ.Division of the National Chemical Research Laboratories, South African Council for Scientific and Industrial Research (Pretoria).(d) X-ray data collection
Preliminary investigations were by standard Weissenberg and precession methods. For the photographic work a Seifert X-ray generator, using Ni-filtered monochromatic CuKo radiation(X = 1.5418A), was employed. The Space Group was determined from the systematic absences, and cell constants were measured from the photographs.
Refined cell constants were obtained during data collection on a Philips. PW1100 four-circle diffractometer with MoKo (X= 0.7107A) or CuKo (X= 1.541SA} graphite-monochromated radiation, using u/28 scans. The cell constants were obtained by least-squares refinement of the 8 values of 25 general reflections in the measured 9 range. During data collection, the intensity of certain standard reflections were checked at intervals, to ensure that crystal deterioration was not observed. The data collection was performed at the National Physical Research Laboratories, South African Council for Scientific and Industrial Research (Pretoria).(e) Crystallographic Computing Programs
SHELX82: Program for Crystal Structure Determination, by G. Sheldrick - used for structure solution and refinement.
XANADU : Program for crystallographic calculations by P.Roberts and G. Sheldrick - used to calculate torsional angles and the best least-squares plane through atoms, with deviations of atoms from the mean plane.
Appendix B (contd)
DIFABS : Program for correcting diffractometer data forabsorption effects, by N. Walker and D. Stuart, a adapted by G.J. Kruger ^ - used to correct data for absorption in the case of the Re2 structures. *
ORTEP : A Fortran Thermal-Eclipsord Plot Program forCrystal Structure Illustrations by C.K. Johnson11 - used to plot diagrams of the molecules and unit cells for the crystal structures,
(f) Crystallographic R-indices(i) The internal consistency R-lndex: R is defined as
R = [Z(N.E(w(F(mean)-F)'))/I((W-l).Z(wF' ))]%where the inner summations are over the N equivalent reflections averaged to give F(mean), and the outer summations are over all unique reflections.
(ii) The conventional R , R = z|Fo-Fc|/£|Fo|, where Fo is the observed structure factor, and Fc the calculated structure
(ill) The weighted R, Rw, Rw = l|Fo-Fciwi/Z |Fo|v/i, where w is the weighted used (w = k/(o*F), k being redetermined after each structure factor calculation).
Appendix C
Torsional Angles for the M-fCQ)^ (L) Structures (M = Re,L s RNC, n = 1-d; M = Mn, L = RNC, n= 2,4; M = Re, L = PMSgPh,
The program XANADU, written by Paul Roberts and G. Sheldrick, was used to calculate torsional angles for the M2{CO)10_n <L)n structures, using tne SHELx"48 output of the final atomic co-ordinates from the crystal structure determinations to perform the calculations.
The torsional angle C(n)-Re(l)-Re(2)-C(m) is defined as the angle between the vector Re(l)-C(n) and the vector Re(2)-C(m), when viewed down Re(l)-Re(2j. The sign of the torsional angle is positive if Re(l)-C(n) is to be rotated clockwise into Re(2)- C(m), and negative if anticlockwise.
In the case of the structure dia.yf Re„(CO)a(PHe^PhJ^] (VII). the C(x)-Re-P-C(y) torsional angles are - '-ly defined.
Torsional angles (°) are listed "ruetures:-(I) Reg(CO)g(CNBu )(II) Re2(C0)a(CNC6H3He2-2,6)2(III) Re2(CO)7(CNMe)3(IV) Re2 (CO)6 iCNC6H3Me2-2,6)4(V) Mn2(C0)8 (CNBut)2(VI) MNZ!CO)6 (CNC6H3Me2-2,6)4(VII) diax[Re2 (C0)8(PMe2Ph)2 )
(I) Re„(CO>:)(CNBut) (II) ReJCO^CCNC^rLMe .-2,6L
C(l)-Re(l)-Re{2)-C(S) CN(i;-.Re(l)-Re(2MW) 137.6C(l)-Re(l)-Re(2)-C(G) -45.1 CN(l)-Re(l)-Re(2)-CO(5) 46.6C(1)-Re(1)-Re(2)-C(7) 166.9 CN(l)-Re(l)-Re(2)-CO(6)C(l)-Re(l)-Re(2)-C(8) -138.2 CN(1)-Re(l)-Re(2)-C0(7) -44.9C (1)-Re(1)-Re(2)~C(9) 135.8 CN(l)-Re(2>-Re(2)-CO(8)C(2)-Re(l)-Re(2)-C(5) -57.4 C0(l)-Re(l)-Re(l)-CN(2)C{2)-Re(l)~Re{2)-C(6) -145.2 CO(1 )-Re(2)-Re(2)-C0{5) 134.8Ct2}-Re(l)-Re(2)-C(e) 121.6 C0(l>-Re(2)-Re(2)-C0(6) -46.2C(2)-Re(l!-Re(2)-C(9) 35.6 C0(l)-Re(l)-Re(2)-C0(7) 43.4
• ■ fC(3)-Re(l)~Re(2j“C(5J 132.9 C0{lJ-Re(l)-Re(2)-C0(8) -170.6C(3)-Re(l)-Re<2)-C(6j 45.1 CO(2)-Re(l)-Re(2)-CN(2)C(3)-Re(l)-Re(2)-C(7) -113.0 CO(2)-Re(1)-Re(2)-CO(5)C(3)~Re(l)-Re(2)-C(S) -48.1 C0(2)-Re(l)-Re(2)-C0(6)C(3)-Re(l>-Re(2)-C(9) -134.1 C0(2)-Re(l)-Re(2)-C0(7) -144.8C(4)-Rea)-Re(2)-C(5) CO(3)-Re(1)-Re(2)-CN(2) 49.3C(4)-Re(2)-fle{2)-C{6) -134.9 CO{3)-Re(1)-Re(2)-CO(5) -41.7C(4>-Re(l)-Re{2)-G(7) CO{3)-Re(1)-Re(2}-CO(6)C(4)-fle(2)-Re(2)-C(8) 131.9 CO(3)-Re(1)-Re(2)-CO(7)C(4)-Re(l)-.Re(2)-C(ti) 45.9 CO(3)-Re(1)-Re(2)-CO(8)C(10)-ReU)-Re(2)-C(5) -137.4 C0(4)-Re(l)-Re(2)-CN(2) -43.0C(10)-Re(l)-Re(2)-C(6) 134.8 C0(4)-Re(l)-Re(2)-C0(5) -134.0C(10)-Re(l)-R6(2)-C(7) -23.2 CO{4)-Re(1>-Re(2)-CO(6) 45.0C(10)-Re(l)-R6(2)-C{8) 41.6 C0(4)-Re(l)-Re(2)-C0(7) 134.5C(10)-Re(l)-Re(2)-C(9) -44.4 C0(4)-Re(l)-Re(2)-C0(8) -79.4
i '
a ■
(III) Re.fCOUCMMe^ (IV) Re„(CO)c(CNCcH;]Me„
C(l)-Re(l)-Re(2)-0(6) C(l)-Re-Re'-G(2)1 -98.0C(l)-Re(l)-Re(2)-C(7) -37.8 C(l)-Re-Re'-C(3)' 171.4C(i)-Re(l)-Re(2)-C(9) 53.7 C(l)-Re-Re'-C(4)' -8.6C(1)-Re(1)-Re(2)-C(10) 140.6 C(l)-Re-Re'-C(5)' 84.1C(2)-Re(l)-Re(2)-C(5) -133.0 C(2)-Re-Re'-C(l)' -"-95.9C(2)-Re(l)-Re(2)-C(6) -44.3 C(2)-Re-Re'-0(2)1 -48.9C(2)-Re(l)-Re(2)-C(7) 45.9 C(2)-Re-Re'-C(3)1 -139.4C(2)-Re(l)-Re(2)-C(9) C(2)-Re-Re’-C(4)1 40.6C(2)-Re(l)-Re(2)-C(lC) C(2)-Re-Re'-C(5)' 133.2C(3)-Re(l)-Re(2)-C(5) C{3)-Rc-Re’-C{l)'
C(3)-Re(l)-Re(2)-C(6) G(3)-Re-Re1-C(2)' -139.4C(3)-Re{l)-Re(2)-C(7) -135.3 C(3)-Re-Re'-G(3)1 130.0C(3)-Re(l)-Re(2)-C(9) C(3)-Re-Re‘-C(4)' -50.0C(3)-Re(l)-Re(2)-C(10) 43.1 C(3)-Re-Re'-0(5)'C(4)-Pe(l)-Re(2)-C(5) 136.9 C(4)-Re-Re'-C(l)1C(4)-Re(l)-Re(2)-G(6) -134.4 G(4)-Re-Re'-C(2)1C(4)-Re(l)-Re(2)-C(7) -44.2 C(4)-Re-Re1-C(3)1 -50.0C(4)-Re(l)-Re(2)-C(9) 47.3 C(4)-Re-Re'-C(4)1 130.0C(4)-Re(l)-Re(2)-C(10) 134.2 C(4)-Re-Re’-0(5)' -137.3C(8)-Re(t)-Re(2)-C(5) -44.4 C(5)-Re-Re1-0(1)' 86.2C(8)-Re(l)-Re(2)-C(6) 44.3 C(5)-Re-Re'-0(2)1C(8)-Re(l)-Re(2)-C(7) 134.5 C(5)-Re-Re'-C(3)'C(8)-Re(l)-Re(2)-C(9) -134.1 C(5)-Re-Re'-0(4)' -137.4C(S)-Re(l)-Re(2)-C(20) -47.1 C(5)-Re-Rel-C(5)1 -44.7
a Atom Re' is related to atom Re by a 2-fold axis, generating the equivalent position (i-x, i-y, z), and similarly for C(n)' and C(n) atom'j (n = 1-5)
(V) Mn (C0)„ CNBu*)_ (VI) Mn:(C0)c(CN0cH
C(l)-Mn(l -Mn(2 -C(6) 46.1 C(l)-Mn-Mn -C(l)1 45.0C(l)-Mn(l -Mn(2 -C(7) -36.1 C(l)-Mn-Mn -0(2)'C(l)-Mn(l -Mn(2 -C(8) 137.0 0(1)-Mn-Mn -0(3)' ^137.0C(l)-Mn{l -Mn{2 -G(9) -43.7 C(l)-Mn-Mn -0(4)' -134.8G(l)-Mn(l -Mn(a -0(10) -134.2 0(1)-Mn-Mn -0(5)' -43.7C(2)^iln(l -Hn(2 -C(6) 13^.1 0(2)-Mn-Mn -0(1)' 114.1C(2)-Mn{l -Mn(2 -C{7) 50.0 0(2)-Mn-Mn -0(3)' -153.9C{2)-Mn(l -C(8) -137.0 C(2)-Mn-Mn -0(4)'C(2)-Mn(l -Mn(2 -0(9) 42.3 0(2)-Mn-Mn -0(5)'C(2)-Kn(l -Mn(2 -C(IO) -48.1 0(3)-Mn-Mn -0(1)' 137.0C(3)-Mn(l -Mn(2 -C(6) C(3)-Mn-Mn -0(2)' -153.2C(3)-Mn(l -Mn(2 -C{8) -11.4 C(3)-Mn-Mn -0(3)' -131.0C(3)-Mn{l -Mn(2 -C(9) 167.9 0(3)-Mn-Mn -0(4)' -42.8
G(3)-Mn(l -Mn{2 -C(IO) 77.5 C(3)-Mn-Mn -0(5)' 48.4C(4)-Mn(l -Mn(2 -C{6) -44.9 0(4)-Mn-Mn -0(1)' -134.8C(4)-Mn(l -Mn(2 -C(7) -127.1 0(4)-Mn-Mn -0(2)’ -64.9C{4)-Mn(l -Mn(2 -0(8) 46.0 0(4)-Mn-Mn -0(3)' -42.8C(4)-Mn(l -Mn(2 -0(9) 0(4)-Mn-Mn -0(4)’ 45.5C(4)-Mn(l -Mn{2 -0(10) C(d)-Mn-Mn -0(5)' 136.6C(5}-Mn(l -Mn(Z -C(6j C(5)-Mn-M.i -0(1)' -43.6C(5)-Mn(l -Mn(2 -0(7) 0(5)-Mn-Mn -0(2)'C(5)-Mn(l -Mn(2 -0(8) -45.5 0(5)-Mn-Mn -0(3)’ 48.4C(5)-Mn(l -Mn(2 -0(9) 133.8 0(5)-Mn-Mn -0(4)' 136.6C(5)-Mn(l -Mn(2 -0(10) 43.3 0(5)-Mn-Mn -0(5)' -132.3
a Atom Mn1 is related to atom Mn by a 2-fold axis, generating the equivalent position Cj-x, j-y, a), and similarly for the C(n)' and C(n) atoms (n = 1-5)
(VXD d ia x [R e J C O )X P M ^ P h )J
C(n)-Re(1)-Rel-C(m)a , 0(x)-Re-P-C(v)
P-Re-Re'-C(l)1 -172.1 C(1)-Re-P-C(5)
P-Re-Re'-CCa)1 97.5 C(1)-Re-P-C(6)
P-Re-Ra'-C(3)1 -81.2 C(1)-Re-P-C(7) „ 0-0P-Re-Re'-0(4)' C(2)-Re-P-C(5)
C(1)-Re-Re'-P1 . C(2)-Re-P-C(6)
C(1)-Re-Re'-C(l)1 C(2)-Re-P-C(7)
C(1)-Re-Re'-C(2)1 C(3)-Re-P-C(5)
C(1)-Re-Re'-C(3)1 C(3)-Re-P-C(6)
C(1)-Re-Re'-C(4)' -49.9 C(3)-Re-P-C(7) -91.1
C(2)-Re-Re‘-P1 57.7 C(4) -Re-P-C(5) -64'0
C(2)-Re-Re'-C(1)1 37.0 C(4)-Re-P-C(6) 55.0
C(2)-Re-Re '-C(2) ' C(4)-Re-P-C(7)
C(2)-Re-Re'-C(3)'C(2)-Re-Re'-C(4) 1C(3)-Re-Re!-P'C(3)-Re-Rel-C(1)1C(3)-Re-Re'-C(2)1C(3)-Re-Re'-C(3)' -50.8C(3)-Re-Re'-C(4)1 40.9C(4)-Re-Re'-Pl 10.7C(4)-Re-Re'-C(1) ' -50.0C(4)-Re-Re'-C(2) 1 -140.4C(4)-Re-Re'-C(3)1 40.9C(4)-Re-Re'-C(4)1 132.6
S Atom Re' is related to atom Re by a 2-fold axis, generatiiti; the equivalent position (x,y,i-z), and similarly for atoms P' and P and C(n)1 and C(n) (n = 1-4).
Appendix D
Structure Factor Tables
The Structure Factor Tables from the ten crystal structure determinations are bound as a separate volume (105 pages).
List of Contents
Code name {no cf pages) Structure
LS2H (9) Cn-C5tt5C02Ms)Cr(CO;2(CNBut)C P m (4) (n-C5H5)Mn(C0)2(CNBut)FEME (6) F'.'< CO) j(CNMe)_RECO (8) Re2(C0)9(CNBu ) (I)REX2 (20) Re2(C0)e (CNC6H3Me2-2,6)2 (II)REH3 (15) Re2(C0)7(CNMe)3 (III)REX4 (13) Re2(C0)6(CNC6H3Me2-2,6)4 (IV)MNTB (16> Mn2(CO)8 (CNBut)2 (V)MNXY (?) Mn2(C0)6(CNC6H3Me2-2,6)4 (VI)REP2 (7) diax[Re2(CO)g(PMe2Ph)2] (VII)
Appendix
List of Publications
The following is a list of publications that have arisen from the work carried out in this thesis.
(a) G.W. Harris, M.O. Albers, J.C.A. Boeyens and N.J. Coville, "Metal Dlr-ers as Catalysts: S. Catalytic Synthesis of(n-Arene)Cr(CO)„(CNR) and the Crystal and Molecular Structure of (n-CgHgC02Me)Cr(C0)2(CNBut)," Organometalllcs.2 (1983) 609.
(b) G.W. Karris, J.C.A. Boeyens and N.J. Coville, "Structure of Dimethylisonitriletr‘,carbeny2irort(0): Fe(CO)g(CNCHg)g," Aota Cryst., C39 (1983) 1180.
(c) G.W. Harris, J.C.A. Boeyens and N.J. Coville, "Catalytic Synthesis of (n^CgHg)Mn(CO)g(CNB) complexes and the Crystal and Molecular Structure of (n-CgHg)Mn(CO)g(CNBu^),"J. Organomet. Chem., 255 (1983) 87.
(d) M.O. Albers, J.C.A. Boeyens, N.J. Coville and G.W. Harris, "Synthesis and Crystal Structure of t-butylisocyanidenona- carbonyldirhenium(O): Reg(CO)g(CNBu^)," J. Organomet. Chem., 260 (1984) 99.
(e) D.J. Robinson, G.W. Harris, J.C.A. Boeyens and N.J. Coville,"A Structural and Kinetic Investigation of the Isomers of M2(C0)g(CNBut)2 (M o Mn.ReJ," J. Chem. Soc., Chem. Conmtun.,(5984) 1307.
(f) G.W. Harris and N.J. Coville, "The PdO catalysed reaction between [Reg(CO)^] and isontriles," Orsanometalllcs,4, (1985) 908.
(g) G.W. Harris, J.C.A. Boeyens and N.J. Coville, "Synthetic substitution of [Re2(C0)10). The crystal and molecular structures of a series of ( R e ^ C O ^ g ^ C N R ) ^ complexes(n = 1, R = tBu; n =• 2,4, R = 2,6-MegCgH^; n = 3, R = Me)," Organometallics, 4, (1985) 914.
Appendix E (contd)
G.W. Harris, J.Ci.A. Boeyens and N.J. Coville, "The Pd catalysed reaction between Re2(CQ)10 and phoephines and the crystal and mcZsmlar structure of diax-Re^(CO)g(PMe^Ph)g J. Chem. Soc.. Dalton Trans., submitted. ^G.W. Harris and N.J. Coville, "ROgCCO}^ and its derivatives, Coord. Chem. Rev., in preparation.N.J. Coville, G.W. Harris and D. Rehder, "Synthesis and characterisation of a series of Vamdium isonitrile complexes," J. Organomet■ Chem., 293, (1985) 365.
D.J. Robinson, G.W. Harris, J.C.A. Boeyans and N.J. Coville, "A kinetic investigation of the reactions of (M = Mn.fle) with isonitriles, and the crystal and molecular structures of Mn2(C0)a(CNBut)2 and Mn2(CO)6(GNCgH^Meg-S,6)^," J. Chem. Soc., Dalton Trans., in preparation.P.D. Harvey, I.S. Sutler, N.J. Coville and G.W. Harris, "Application of Raman microprobe technique (MOLE) to the study of vibrational spectroscopy of rhenium carbonyl and its isonitrile derivatives," Can. J. Chem.. in preparation.
'.Mtlecular Mechanics Calculations
Iii oh XI-V, Che results of the X-ray crystal structure determinations of a series of dirhenium ca rb o n y - is oni tr il e complexes viz. Ke^artgtcmV) (I)', Ke2(CO)g< mc6H3Me2-2,6)2 (II) K62(C0)7(CIMe)3 (III) and Re2(CO)(.(CNC6H3Me2-2,6)^ (IV), were presented. In order to quantify the relative importance of the various steric and electronic factors in these structures, molecular mechanics calculations were performed on the complexes (I) - (IV).
The molecular mechanics calculations were carried out using the Energy Minimization Program EMPMDS2®^, written by M.I.J. Haneef, and based onthe molecular mechanics program of White* based on that developed by Koolman et 287
The force field used was (see equation I)
+ E ^ - 3 i t JJJL (I)"j'li % "li
The sources of the force field parameters are discussed below.
(a) Won-bonded parameters
The non-bonded parameters were based on the Lennard-Jones potential (see equation II).
(n»-Y)I
V(r) 12
where A = /e* (2r*) and B = /e* (2r*)2
r* is the van der Waals minimum, and e* the \ (see Figure E.1).
i der Waals well depth
Figure E. 1 ■ ...Plot of V(r) against r, showing r* and e*.
Table E.1 : Values of the force field parameters used in the calculations.
E.1.1. r* and e*
Atom type_________________r*(A) __________e*(kcal/mol)cC(CN)0N 1.750Re 2.76)
E.1.2. Kr and
Bond Type Kr (kcal/mol A2)C 0 1.130C Re 1.987C N (double) 1.130
(single)C C (single) 1.552
(aromatic) 1.388
Angle type Kg(kcal/mol rad ) v°>eqOC-Re-COeq trans " 58.0
eis 58.0axOG-Re-COeq 58.0 93.7 •eqOC-Re-CN trans 58.0 174.9
=t. 58.0 89.9axOC-Re-CN 58.0 92.1NC-Re-CN 58.0eqCO-Re-Re 58.0axCO-Re-Re 58.0CN-Re-Re 58.0Re-C-O(eq)Re-C-O(ax)Re-C-NC-N-C 90.0N-C-C(eBu) 80.0Ci-C-C(CBu) 63.0C-C-C (benzene) 85.0N-C-C(benzene) 70.0
Table E2 : Observed and calulated Re-Re bond lengths for the Re„(C0),n (CNR) (n = 0-4) structures.
R./CO),0Re2(C0)9(CNB!.C) (I) ' Re2(CO)g(CNC6H3Me2-2,6)2 (II) Re2 (CO)7(CNMe)3 (III) Re2(CO)6(CNC6H3Me2-2,6)4 (IV)
! bond length (A)Crystal Structun
3.041(1) 3.048(1) 3.047(1) 3.049(1) 3.081(2)
The calculated results indicate a slight increase in the Re-Re bond length down the series Re2(CO)^Q_n(CNR)n (n = 1-4), but this effect is not as large as might be expected from the crystal structure data. Hence the role of non-bonded interactions, or steric effects, which might be expected to increase the Re-Re bond length, is not the dominant facftor in these structures. The differences between the crystallographic Re-Re bond distance, and the calculated values, can be ascribed to electronic effects which are not adequately modelled by using the force field for the parent Re^CO)^. In particular, replacing carbonyls by isonitriles, which are poorer v-acceptors^, would be expected to cause a weakening, and hence a lengthening, of the Re-Re bond. Hence electronic i.e. bonding interactions, rather than steric effects i.e. non-bonded interactions, would appear to be the dominant factor influencing the length of the Re-Re bond in the Re2(C0)10_n(CNR)n structures .
349f
The values of r* and e* for the C,0 and N atoms were obtained from Kollman^8 . For Re, the r* value was taken as the shortest Re-Re distance in rhenium metal^88. The values of r* and £* used in the calculations are given in Table E.1.1.
(b) Bond length and bond angle parameters.The values for the equilibrium bond length req, and bond angle 6^, were obtained from X-ray crystal structures of Re^(CO)^^8 , and Re2(CO)10_n (CNR)n (ch XIV). For the parent compound, Re2(CO)]0, the Re-Re equilibrium bot.d distance was adjusted until the observed structure of Re2(C0)10'^8 was reproduced (Kr = 118 kcal mol A2). This value of ret[ (Re-Re) (3.048A) was then used in the subsequent calculations for the Re2(CO) 10_n (CNR)n(n = 1-4) derivatives. The values of r ^ and 8 ^ used in the calculations are given in Tables E.1.2 and E.1.3 respectively.
(c) Force constants.
The bond and angle force constants, K' and Kg, were obtained from lAfrared ^ and Raman1*7*3 Spectroscopic studies on Re2(CO)^Q. The value used
for the force constant for Che Re-Re bond was 118 kcal/mol A2 , obtained from the Raman study of R e ^CO)^ by Spiro et al1*7*3. The values of the force constants Ke and Kg used in the calculations are given in TablesE.1.2 and E.1.3 respectively.
The force field parameters were established by an analysis of the pare- t Reg(CO)^ structure, the X-ray crystal structure of which has been reported . These force field parameters were then kept constant for the subsequent calculations on the derived Re2(CO)^_^(CNR)^ (n = 1-4) structures.
Results and discussion.
An analysis of the results revealed a variation in the Re-Re bond length. The values of the bond angles and the other bond lengths did not change significantly. Table E.2 below shows the calculated Re-Re bond lengths, compared to the crystal structure values.
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Organometalllcs, 2 (1983) 144.275. D.G. Dahm and R.A. Jacobson, J . Am. Chem. Soc., 90 (1965) 5106.276. E. Forbes, N. Goodhand, D.L. Jones end T.A. Hamor,
J. Organomet Chem., 182 (1979) 143.277. f?.E. tienfield, B.F.O. Johnson, P.R. Raithby and G. Sheldrick,
Acta Cryst., B34, (1978) 666.
278. R.J. Goudamit, B.F.G. Johnson, J. Lewis, P.R. Ftaithby andK.H. Whitmire, J. Chem. Soc., Chem Common., (1982) 640.
279. N.J. Coville, pgrsonal communication.280. M.R. Churchill and E.G. DeBoer, Inorg. Chem., 16 (1977) 878.281. H.D. Kaesz, R. Bau and M.R. Churchill, J. Am. Chem. Soc.,
89 (1967) 2775. „282. J. Casanova, F.E. Schuster and N.D. Werner, J. Chem. Soc.,
(London). (1963) .4280. .283. W.C. liamilton, Acta Crygt., 18, (1965) 502.284. "incernational Tables for Crystallography Vol. A. Space
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286. D.N.G. White, Computers and Chemistry, Vol. 1, pp 225 - 233 Pergamon Press, (1977),
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CHEMICAL AND STRUCTURAL STUDIES OF SUBSTITUTED TRANSITION
METAL CARBONYL COMPLEXES
APPENDIX D
STRUCTURE FACTOR TABLES
Gillian Wendy Harris
University of the Witwatererend, Johannesburg November 1984
Appendix D
Structure Factor Tables
Code name {no. of pages) Structure Pages
LS2H (9) h -C6H5C02Me)Cr(C0)2 (CNBut) 1-9CPMN (4) (r,5c5H5)'/n(C0)2(CNBut ) 10-13FEME (6) Fe(C0)3{CNMe)„ 14-15RECO (8) RSg(CO)g(CNBu ) (I) 20-27RBX2 (20) Re2 (C0)e{CNC6H3Me2-2,6)2 (II) 28-47REMS (15) Reg(C0)7(CNMe)3 (III) 48-62REX4 (13) Re2 (C0)6(CNC6H3Me-2,6)4 (IV) 63-75MNTB (16) Mn2(C0)8(CNBut)2 (V) 76-91MNXY (7) Mn2 (C0)6(CNC6H3Meg-2,6)4 (VI) 92-98REP2 (7) diax-[Re2(C0)g(PMe2Ph)2) (VII) 99-105
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Author Harris Gillian Wendy
Name of thesis Chemical And Structural Studies Of Substituted Transition Metal Carbonyl Complexes. 1984
PUBLISHER: University of the Witwatersrand, Johannesburg
©2013
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