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Chapter 22 d-block metal chemistry:
the second and third row metals
Occurrence, extraction, and uses
Physical properties
Inorganic Chemistry
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Relative abundances of the second and third row d-block metals in the Earth’s crust. The data are plotted on a logarithmic scale, and the units of abundance are parts per 10
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Trends in the values of standard enthalpies of atomization (298 K)
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yttriumY2O3 YX3 (X = F, Cl, Br, I) Y3+ + 3e- ⇌ Y E° = -2.37 V
C.N. = 9
Coordination compounds C.N. = 6 to 9
YCl3 + 3KCl → K3YCl6
YBa2Cu3O7-x Superconductor
dodecahedral ion [Y(OH2)8]3
zirconium and hafnium
C.N. = 8
[Zr4(OH)8(OH2)16]8
MCl4, MO2: Extended solids w/chains of edge sharing-octahedra or related structures
Cubic zirconia
HfF4 + 3 KF K3[HfF7]∆ in sealed Pt tube
Hf + HfCl4 HfCl1070 K in sealed Ta tube
Hf + HfCl4 HfCl3720 K in sealed Ta tube
(unbalanced)
(unbalanced)
Lower oxidation states of hafnium
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Zr(acac)4
monocapped trigonal prismatic
[ZrF7]3-
[ZrF7]3-
pentagonal bipyramidal
[H3N(CH2)2NH2(CH2)2NH3][ZrF7]
square antiprismatic
in a guanidinium salt
ZrCl4 + 2N2O5 → [Zr(NO3-O,O’)4] + 4NO2Cl
dodecahedral
[Zr6Cl14(PnPr3)4)] [Zr5Cl12(m-H)(m-H)2(PMe3)5]
m-H and m3-H are present in the Zr5 framework
Zirconium clusters
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niobium and tantalum
The linearity of the bridge indicates multiple bond character.
[Ta2OF10]2-
M2O5 (M = Nb, Ta)
MX5 (M = Nb, Ta; X = F, Cl, Br, I)
NbOCl3
The structure of [Nb(OH2)(O)F4]- illustrates how oxo and aqua ligand O atoms can be distinguished.• The Nb-F bonds bend away from the oxido O=Nb bond• Difficult to locate H atoms using XRD
Niobium(V) and tantalum(V) have a variety of coordination environments:trigonal bipyramidal: [Ta(NEt2)5]
square-based pyramidal: [NbOCl4]-
octahedral: [Nb(OH2)(O)(F4)]-
pentagonal bipyramidal: [Nb(OH2)2(O)(ox)2]-
capped trigonal prismatic: K2[MF7] (M = Nb, Ta)
dodecahedral: [M(η2-O2)2F4]3- (M = Nb, Ta)square antiprismatic: Na3[MF8] (M = Nb, Ta)
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niobium(IV) and tantalum(IV)
shortNb-Nb
shortNb-Nb
longNb-Nb
[Nb6I8]3+[M6X12]n+ (n=2 or 3)
3d 2d
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[Nb6Cl18]3-Part of solid state structure of Nb3Cl8
molybdenum and tungsten
MoOF4 WOF4
infinite chains tetrameric units
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[Mo7O24]6- [W6O19]2-
• Common structural features: cage is supported by oxygen bridges and there is no metal-metal bonding
• Cage is constructed from octahedral MoO6-units connected by shared oxygen atoms.
[SiMo12O40]4- [H3S2Mo18O62]5
-Keggin anion -Dawson anion
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-form of MoCl4 consists of cyclic Mo6Cl24 units [Mo3(m3-O)(m-O)3(OH2)9]4
W6Cl18
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Mo2(NMe2)6 Mo2Cl2(NMe2)4 Mo2(OCH2tBu)6
[Mo6Cl14]2 W6Cl18C [Mo2Cl8]4
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technetium and rhenium pH 0
Re3Cl9 [Re3Cl12]3
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two polymorphs of OsOF4
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adduct formed between N-methylmorpholineand OsO4
[Os2(NtBu)4(m-NtBu)2]2
[OsO2(O2CMe)3]
ruthenium and osmium
Partial MO diagram for the interaction between the dxy, dxz and dyz atomic orbitals of the Ru(IV) centers
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Representative complex-forming reactions starting from [OsCl6]2
[Os2Cl8]2-
staggered eclipsed
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[HIm][trans-RuCl4(Im)(DMSO-S)]
[HInd][trans-RuCl4(Ind)2]
(Im imidazole, Ind indazole)
[RuBr3(Et2S)(Et2SO)(NO)] [RuCl(NO)2(PPh3)2]
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rhodium and iridium
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[Ir(NCS-S)6]3 [Ir(S6)3]3
[Rh2(m-O2CR)4] [Rh2(m-O2CR)4L2]
[Rh2(m-O2CMe)4(OH2)2]
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palladium and platinum
PtCl2 --(F2, 620 K) PtF5
-red solidPtF5 disproportionates into PtF4 and PtF6
Platinum blues – mixed valent complexes containing discrete Ptn chains• {Pt4}9+ complex
Tetrameric structure of PtF5
X- CN- I- Br- Cl-
v(Pt-H) (cm-1) 2041 2156 2178 2183 (1H for Pt-H), ppm -7.8 -12.7 -15.6 -16.8
trans-influence
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copper and silver
silver and gold
Part of one chain in the solid state structure of AuSO4, which contains [Au2]4 units; the [SO4]2 act as both bridging and monodentate ligands
[AuL2]2 (L1,4,7-trithiacyclononane)
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[Au2(H2NCH2CH2NHCH2CH2NH2)2]2+ (part of one chain in which dimers are connected by weak AuAu interactions is shown)
trimer [Ag3L3]3 where L is the sulfur-containing macrocycle1,4,7-trithiacyclononane
[Au2(CS3)2]2 [Au2(TeS3)2]2
cadmium and mercury
Solubilities of Hg(II) halides in water