Metal-metal bonded homo- and heterobimetallic compounds of Pt(I) and Pd(I) supported by a bridging-N,P:N',P' moiety of a potentially hexadentate ligand
Jones, ND; Foo, SJ; Patrick, BO; James, BR
| HERO ID | 5416754 |
|---|---|
| In Press | No |
| Year | 2004 |
| Title | Metal-metal bonded homo- and heterobimetallic compounds of Pt(I) and Pd(I) supported by a bridging-N,P:N',P' moiety of a potentially hexadentate ligand |
| Authors | Jones, ND; Foo, SJ; Patrick, BO; James, BR |
| Journal | Inorganic Chemistry |
| Volume | 43 |
| Issue | 13 |
| Page Numbers | 4056-4063 |
| Abstract | Reactions of metal-metal bonded homobimetallic (Pd(2)) and heterobimetallic (PtPd) complexes, supported by a P,P'-bridging-bis(P,N-chelating) coordination mode of the potentially hexadentate ligand 1,1-bis[di(o-N,N-dimethylanilinyl)phosphino]methane (dmapm), with CO, diethylacetylenedicarboxylate (DEAD), and thiols (RSH) in CH(2)Cl(2) are described. At room temperature, rac-Pd(2)Cl(2)(mu-N,P:P',N'-dmapm) gives the stable complexes Pd(2)Cl(2)(mu-CO)(2)(mu-P:P'-dmapm) and PdCl(eta2-DEAD)(mu-P:P',N-dmapm)PdCl (which is fluxional in solution), while rac-PtPdCl(2)(mu-N,P:P',N'-dmapm) disproportionates to PtCl(2)(P,P'-dmapm) and Pd metal, although at low temperature intermediate carbonyl species are detected in the CO reaction. The reactions with thiols in the presence of triflic acid (HOTf) generate rac-[MPdCl(2)(mu-SR)(mu-N,P:P',N'-dmapm)][OTf] and H(2) for both M = Pt and Pd. In CH(2)Cl(2), PdX(2)(dmapm) species (X = halide or CN) exist as equilibrium mixtures of P,P'- and P,N-ligated forms. For X = Cl, the P,P'-P,N equilibrium is governed by DeltaH degrees = -5.5 +/- 0.5 kJ mol(-1) and DeltaS degrees = 10 +/- 1 J mol(-1) K(-1), and the ring-strain energy within the P,P'-isomer is approximately 32 kJ mol(-1); the equilibrium increasingly favors the P,N-form with X = CN > I > Br > Cl. The solid-state structures of rac-[PtPdCl(2)(mu-SEt)(mu-N,P:P',N'-dmapm)][OTf] and PdCl(2)(P,N-dmapm) are presented; the latter contains both bound and free N- and P-atoms of identical types in the same molecule and permits an assessment of sigma- and pi-bonding between these atoms and Pd. |
| Doi | 10.1021/ic040019t |
| Pmid | 15206888 |
| Wosid | WOS:000222165700043 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |