Group IV donors

Group IV Donors. Carbon donor ligands. The preparation of the isocyanide complexes tra s-[Ru(CNEt)2(APh3)2X2] (A = P, As, or Sb X = Cl or Br) 

Cationic y-oxo-isocyanato Ru complexes have been isolated [Ru(CN)J - + 12MeCOMe + 6R,O BF .  

Group IV Donors. C-donor ligands. Treatment of [Ru(CN)6]4- with dimethylsulphate for 6h at 95 °C has produced the white isocyanide complex [Ru(CNMe)6]2 +. 67 Electrochemical studies showed that the corresponding Ru,u species can only exist under strongly oxidizing conditions. Furthermore, addition of simple amines to [Ru(CNMe)6]2+ produces either (11) or (12) (containing either uni- or bi-dentate 

Sandu and A. K. Mehta, Inorg. Nuclear Chem. Letters, 1973, 9, 1197. 

ESCA spectra have been recorded for a series of pyrazine-bridged ruthenium dimers including [(NH3)5Ru(pyz)Ru(NH3)5]s H and [(bipy)2ClRu(pyz)RuCl(bipy)2]3+.50 The data show that both Ru and Ruin are present in those complexes although the metal sites are equivalent. The speed with which ESCA monitors electron distribution (ca. 10 17 s) would seem to make it an excellent spectrosocpic tool for such valence-state assignments. 

Rhodium(lI).—This relatively rare oxidation state is attracting increasing attention, with the isolation and characterization of several new complexes. 

Scollary, Inorg. Chim Acta, 1976,16, Lll. 

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Complexes of platinum(II) with Group IV donor ligands. U. Belluco, G. Deganello, R. Pietropaolo and P. Uguagliati, Inorg. Chim. Acta, Rev., 1970, 4, 7-39 (149). 

Fig. 23. Schematic representation of the group IV donor-hydrogen complex with hydrogen in AB site. The black spheres represent the group V atoms (As), the large white ones the group III atoms (Ga), the small white one the hydrogen atom and the dotted sphere the impurity. The lone pair on the threefold coordinated group V atom is not represented.

Group IV Donors. The preparation of the complexes c/s-[Ru(CNEt)2(APh3)2-(SnCljlCl] (A = P, As, or Sb) for the treatment of c/.s-[Ru(CNEt)2(APh3)2Cl2] with SnCl2, provides another example of insertion of SnCK into a M—Cl bond. The structure (22) was proposed from i.r. data. ... 

Group IV Donors. A H n.m.r. study of the cis-trans isomerization of [OslCO) -(SiMe3)2] indicates that the process is non-dissociative. These species may therefore provide a rare example of stereochemical non-rigidity in nonchelate octahedral complexes. Similar non-rigidity was observed for [Os(CO)4-(SiMeCl ) ] and [Os(CO)4(SnMe3)2]. ... 

Group IV Donors. The reaction of ds-[Pd(PPh3)(PhNC)Cl2] with phenyl derivatives of heavy metals, YPh (Y = HgPh, PbMe, PbPhjCl SnPhj, or BiPhj), has been shown to yield an N-phenylimino-complex ... 

Group IV Donors. A new class of Pt complex of the formula [Pt(PPh3)2-(CNBu )] has been isolated from the reaction between [Pt(PPh3)2(C2H4)] and free isocyanide. Further treatment with CO gave [Pt(PPh3)2(CNBu )(CO)], and comparison of the v(NC) frequencies in these two new complexes suggests that CO is a more effective ji-acceptor than the isoelectronic isocyanide. Oxidative addition reactions were also reported. ... 

Some complexes which satisfy this definition are dealt with elsewhere, however. Those with X or Y as the Group V donors P, As or Sb are dealt with in Chapter 14 of this volume. Those with X or Y = Hg are described in Chapter 11 and the Group IV donors Si, Ge, Sn and Pb are included in Chapter 12.2, With very few exceptions this means that the relevant X,Y combinations are pairs derived from nitrogen, oxygen, sulfur or selenium donor groups. However, some specific examples of these combinations also occur elsewhere in this work. Amino acids (generally N—O bidentates) are covered in Chapter 20.2, Schiff base ligands (N—O or N—S) in Chapter 20.1, and several S—O... 

Group IV Donors. The fulminato complex trans-[Rh(CNO)(PPh3)2(CO)] has been obtained as an intermediate in the formation of the corresponding isocyanato species from frtms-[RhCl(PPh3)2(CO)] and MeN02.143 An alternative safe route to this and other Pdu and Pt11 fulminato species is via attack of (AsPh4)CNO on appropriate substrates.157... 

Group IV Donors. Acidopentacyano-complexes of the type [M(CN)5X]" (M = Rh or Ir X = Cl-, Br-, I-, OH-, or NCMe) have been readily prepared using the sequence (45).209 An analysis of their u.v.-visible spectra in aqueous solution estab-... 

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