Group V Donor Ligands

Group V Donor Ligands. Octahedral complexes [M(tdta)2Cl2] (M = Pd or Pt tdta = l,3,4-thiadiazole-2-thiol-5-amine) have been prepared (see p. 364).  

Nitrosation of ethylenediamine complexes [PtenajC and trans-[Pten2Cl2]Cl2 gives [Pt(NO-en—H)3] and [Pt(N0-en—H)2(N02)Cl], respectively. Tetrapyridine complexes [Pt(py)4]X2 (X = Cl or Br) are converted into [Pt-(py)4X2][H(N03)2]2 or [Pt(py)4][112(804)2] on treatment with nitric or sulphuric acids. The former complex gives orange [Pt(py)3Br3]Br on treatment with excess KBr, but yields the pale brown [Pt(py)4l2]l2 with KI. 

Association between [Pt(N-N)3] [(N-N) = en or pn] and the anions F, Cl , Br , I , SO4 , sol , SeOa, SjOj , and CO has been studied using spectro-photometric, solubility, and thermochemical methods. 

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TETRACARBONYLIRON(0) COMPLEXES CONTAINING GROUP V DONOR LIGANDS... 

B. OTHER TETRACARBONYL (GROUP V DONOR LIGAND) IRON(O) COMPLEXES... 

The catalytic substitution reactions of metal carbonyl clusters, including [M3(CO)i2] (M = Fe, Ru, or Os), [Ru4H4(CO)i2], [Rh6(CO)i6], and [Co3(CO)9(/it-CCl)], with isocyanides or Group V-donor ligands may be induced by either electrochemical or chemical (benzophenone ketyl) reduction. The most favorable conditions for efficient substitution include (1) the formation of a radical anion with a significant lifetime and (2) the use of a ligand which is not reduced by [Ph2CO], and which is less of a tt acid than CO (166). 

FIG. 21. chemical shift chart for diamagnetic V — i). V(0). V( +i), and V( +v) compounds relative to external VOCI3, positive values indicating relative deshielding. Abbreviations Cp = cyclopentadienyl, L = Group V donor ligand. (189)... 

Group V Donor Ligands. iV-Allylpyrazolyl complexes of Ag, Cu, Co", Cu", and Zn" have been reported. I.r. spectra show that [Ag(AP)]N03 is co-ordinated through N and the double bond, while the complexes of the bivalent metals are bonded only through N. 

This section is divided into two parts dealing with (I) the bonding and (2) the stereochemistry of complexes containing Group V donor ligands. 

Transition-Metal-Promoted Reactions of Unsaturated Hydrocarbons. IV. Reactions of Norbornenyl Complexes of Palladium(II) with Group V Donor Ligands, Olefins, 1,3-Dienes and 1,2-Dienes, E. Ban, R. P. Hughes, and J. Powell, J. Organometal. Chem., 69, 455 (1974). 

Tetracarbonyliron 0) Complexes Containing Group V Donor Ligands 169... 

Group V donor ligands react with [CpRu(CO)2l] in the presence... 

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