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DOI: 10.1039/A900390H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2159-2170

Heterobimetallic alkoxysilyl cationic complexes: investigations into the displacement of a µ-η2-Si,O bridge by functional phosphine ligands

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Joël Blin, Pierre Braunstein, Jean Fischer, Guido Kickelbick, Michael Knorr, Xavier Morise and Tobias Wirth

Abstract

The lability of the SiO→M interaction unique to some bimetallic complexes may confer hemilabile properties to the Si(OR)3 ligand and various bifunctional phosphines P–Z have been used in order to evaluate the possible competition for co-ordination between the bridging SiO→M interaction and P–Z chelation. Thus, treatment of the heterobimetallic complexes [(OC)3[upper bond 1 start]Fe{µ-Si(OMe)2([lower bond 1 start]OMe)}(µ-dppm)M[lower bond 1 end][upper bond 1 end]Cl] (M = Pd 4 or Pt 6; dppm = Ph2PCH2PPh2) and [(OC)3[upper bond 1 start]Fe{µ-Si(OMe)2([lower bond 1 start]OMe)}(µ-dppa)P[lower bond 1 end][upper bond 1 end]dCl] 5 (dppa = Ph2PNHPPh2) with TlPF6 in the presence of P–Z afforded the corresponding cationic compounds [(OC)3[upper bond 1 start]Fe{µ-Si(OMe)2([lower bond 1 start]OMe)}(µ-dppm)M[lower bond 1 end][upper bond 1 end](P–Z)PF6 (M = Pd 1 or Pt 3) and [(OC)3[upper bond 1 start]Fe{µ-Si(OMe)2([lower bond 1 start]OMe)}(µ-dppa)P[lower bond 1 end][upper bond 1 end]d(P–Z)]PF62 (P–Z = Ph2PC6H4(o-OMe), a P{C6H4(o-OMe)}3, b Ph2PCH2C(O)Ph, c Ph2PCH2CH[double bond, length half m-dash]CH2, d Ph2P(CH2)2CN, e or Ph2PCH2C(O)NPh2, f[hair space][hair space]). These complexes are stabilized by the occurrence of a Fe–Si-O→M four-membered ring and the pre-existent SiO→M interaction in 4–6 was not displaced by the donor function of the incoming P–Z ligand. Complexes 1b and 1f were obtained as mixtures of two isomers, the P–Z ligands acting either as monodentate or as a P,O chelate. In the latter cases formation of five-co-ordinated palladium species is proposed. Displacement of the SiO→Pd interaction originally present in 4 was observed when the diphosphines (Ph2P)2NR (R = Me or (CH2)3Si(OEt)3) were used, since the two phosphorus atoms co-ordinate to the Pd. Surprisingly these diphosphine ligands show different co-ordination modes, depending on whether dppa or dppm is used as the assembling ligand. In the former case, chelation to the Pd is observed, which leads to complex [(OC)3{(MeO)3Si}[upper bond 1 start]Fe(µ-dppa)[lower bond 1 start]P[upper bond 1 end]d{Ph2PN(Me)P[lower bond 1 end]Ph2}]PF62g, whereas in the latter case, oligomeric entities of the type [{(OC)3{(MeO)3Si}[upper bond 1 start]Fe(µ-dppa)P[upper bond 1 end]d[Ph2PN(R)PPh2]}n][PF6]n1g,1h (n probably equals two) were formed. The molecular structures of [PdCl(dppm-P,P′){Ph2PC6H4(o-OMe)}]PF6 g and [Pd2Cl2(µ-CO)(µ-dppm)2] 10, obtained during this work, have been determined by X-ray diffraction.

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