2 Homometallic Alkoxides

216 Alkoxo and Aryloxo Derivatives of Metals
Table 3.4 (Continued)
Synthetic Characterization
Compound route 1 techniques References
Pentaalkoxometallate derivatives
M0fTi⊲OPri⊳5gn M
A-1 MW, IR, NMR, X-ray 41, 60, 225
0 D Li; n D 2.
M0 D Na, K; n D1
[M0fM⊲OBut⊳5g]2 A-1
M0 D Li, Na; M D Ti, Zr MW, volatility, 41, 60
M0 D K; M D Zr NMR, X-ray 41, 182
M0 D K, M D Sn⊲IV⊳ NMR, X-ray 56
fTi⊲OPri⊳5gBafTi2⊲OPri⊳9g A-2 IR, NMR, X-ray 81
[I2SnfTi⊲OPri⊳5g2] C IR, NMR, X-ray 236
[I3SnfZr⊲OPri⊳5g.PriOH] Hexaalkoxometallate derivatives
C IR, NMR, X-ray 236
SnZr⊲OPri⊳6 A-2 119Sn NMR 82
M0Zr⊲OBut⊳6 A-2 119Sn NMR 82
M0 D Sn⊲II⊳, Pb 207Pb NMR 82
SnIISnIV⊲OPri⊳6 C 1 119 H, Sn NMR 226
[Na2fZr⊲OCH⊲CF3⊳2⊳6g.C6H6] A-1, C NMR, X-ray 227
[f⊲COD⊳Rhg2fSn⊲OEt⊳6g]
[f⊲COD⊳Rhg2fTi⊲OPr
C NMR, X-ray 229
n⊳6g] Tl2Sn⊲OEt⊳6
[⊲dme⊳2Na2Ce⊲OBu
C
A-1
NMR, X-ray
NMR, X-ray
230
55
t⊳6] [BaZr⊲OBu
C NMR, X-ray 228
t⊳6⊲thf⊳2] [BaZr⊲OH⊳⊲OPr
A-1 IR, NMR 83
i⊳5⊲PriOH⊳]2 Heterotrimetallic alkoxides
A-1 IR, NMR 83
[Cd⊲OPri⊳3BaM2⊲OPri⊳9]2 M D Ti, Zr, Hf
A-1, C NMR, X-ray 136, 160, 162
[Cd⊲OPri⊳3SrfZr2⊲OPri⊳9g]2 A-1, C NMR, X-ray 235
[fZr2⊲OPri⊳9gMfAl⊲OPri⊳4g] C IR, NMR, MW, UV-Vis 8, 9, 101, 109
M D Mn, Fe, Co, Ni 156–159
fAl⊲OPri⊳4gBefZr⊲OPri⊳5g C IR, NMR, MW 7
[fZr2⊲OPri⊳9gFefTa⊲OPri⊳6g] C MW, volatility 109
[fAl⊲OPri⊳4gFefZr2⊲OPri⊳4g2] C MW, volatility 9
[YfAl⊲OPri⊳4gxfZr2⊲OPri⊳9g3 x D 1, 2
x] C 1 13 89 H, C, Y NMR 222
1 See Section 2 for details of routes listed.
3.4.2 Different Modes of Bonding of Nona-alkoxodimetallate(IV) ligands
3.4.2.1 Tetradentate mode of coordination
A critical survey of a large number of derivatives with fM2⊲OR⊳9g ligands suggests
an idealized core structure (Fig. 3.5) in which all the metals attain a six-coordinate
state.
Factors such as size of M, size, valency, and preferred coordination state of M 0 ,and
bulk of the alkoxo group(s) determine the requirement for additional L...L ligands (as
a bidentate neutral ligand) or zero/one/two monovalent unidentate ligand(s) on M 0 .