Coordination chemistry of and -, Y = S or Se, R = Ph or tBu: rhodium, iridium and ruthenium complexes; 13C, 31P, and 77Se NMR studies; and the crystal and molecular structures of tBu2)-P,S>>BF4*CHCl3 ...

Article abstract of DOI:10.1016/0022-328X(93)83192-X

Reactions of the chloro-bridged complexes, , M = Ir or Rh, COD = cyclooctadiene, with CH2(PPh2)(P(Y)R2), Y = S or Se, R = Ph or t-Bu, provide a synthetic route to the cations, >⁺, which are isolated as fluoroborate or perchlorate salts.Treatment of these products with sodium hydride results in facile deprotonation to the neutral complexes, >, and when Y = S, the neutral complexes are also accessible via reactions of with Li.Reactions of the cations, >⁺ with other ligands, Lg = (CO)2, (CNt-Bu)2 or bis(diphenylphosphino)methane (dppm), result in displacement of cod to form >⁺.Ruthenium complexes of CH2(PPh2)(P(S)Ph2) are accessible via similar bridge cleavage reactions using , L = benzene or p-cymene.These complexes are characterized by complete 13C, 31P, and 77Se nuclear magnetic resonance (NMR) studies and by four crystal structure determinations.The complexes >BF4*CHCl3 (1), >ClO4*CH2Cl2 (2), > (3) and >*CH2Cl2 (4) crystallize in the P<*> (No. 2) space group (Z = 2) with respective unit cells: a = 12.307(7) Angstroem, b = 14.743(8) Angstroem, c = 10.877(6) Angstroem, α = 74.42(5) deg, β = 107.65(6) deg, γ = 105.47(5) deg; a = 12.163(1) Angstroem, b = 14.56(1) Angstroem, c = 10.560(1) Angstroem, α = 77.69(1) deg, β = 74.54(1) deg, γ = 77.01(1) deg; a = 10.650(4) Angstroem, b = 13.327(4) Angstroem, c = 10.419(3) Angstroem, α = 90.60(3) deg, β = 102.64(3) deg, γ = 83.15(3) deg; a = 11.217(2) Angstroem, b = 17.124(3) Angstroem, c = 10.412(2) Angstroem, α = 90.58(1) deg, β = 112.29(2) deg, γ = 97.53(2) deg.Complexes 1-3 all contain bidentate P,S-bonded ligands occupying two coordination positions of an approximately square planar metal centre.In each case, the coordination is completed by two double bonds of a cod ligand.In contrast, complex 4 contains a monodentate P-bonded ligand.