@article {898,
	title = {Metal-metal bonded homo- and heterobimetallic compounds of Pt(I) and Pd(I) supported by a bridging-N,P : N {\textquoteright},P {\textquoteright} moiety of a potentially hexadentate ligand},
	journal = {Inorganic Chemistry},
	volume = {43},
	number = {13},
	year = {2004},
	note = {ISI Document Delivery No.: 831AQTimes Cited: 11Cited Reference Count: 55},
	month = {Jun},
	pages = {4056-4063},
	type = {Article},
	abstract = {Reactions of metal-metal bonded homobimetallic (Pd-2) and heterobimetallic (PtPd) complexes, supported by a P,P{\textquoteright}-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 (FISH) in CH2Cl2 are described. At room temperature, rac-Pd2Cl2(mu-N,P:P{\textquoteright},N{\textquoteright}-dmapm) gives the stable complexes Pd2Cl2(mu-CO)(2)-(mu-P:P{\textquoteright}-dmapm) and PdCl(eta(2)-DEAD)(mu-P:P{\textquoteright}, N-dmapm)PdCl (which is fluxional in solution), while rac-PtPdCl2(mu-N,P:P{\textquoteright}, N{\textquoteright}-dmapm) disproportionates to PtCl2(P,P{\textquoteright}-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-[MPdCl2(mu-SR)(mu-N,P:P{\textquoteright},N{\textquoteright}-dmapm)][OTf] and H-2 for both M = Pt and Pd. In CH2Cl2, PdX2(dmapm) species (X = halide or CN) exist as equilibrium mixtures of P,P{\textquoteright} and P,N-ligated forms. For X = Cl, the P,P{\textquoteright}-PN equilibrium is governed by DeltaHdegrees = -5.5 +/- 0.5 kJ mol(-1) and DeltaSdegrees = 10 +/- 1 J mol(-1) K-1, and the ring-strain energy within the P,P{\textquoteright}-isomer is similar to32 kJ mol(-1); the equilibrium increasingly favors the P,N-form with X = CN much greater than I > Br > Cl. The solid-state structures of rac-[PtPdCl2(mu-SEt)(mu-NP:P{\textquoteright},N{\textquoteright}-dmapm)][OTf] and PdCl2(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.},
	keywords = {A-FRAME COMPLEXES, BINUCLEAR COMPLEXES, COORDINATION CHEMISTRY, MOLECULAR-STRUCTURES, OXIDATIVE CARBONYLATION, PD DINUCLEAR COMPLEX, PLATINUM COMPLEXES, RING STRAIN ENERGIES, STRUCTURAL SYSTEMATICS, TERTIARY PHOSPHINE-LIGANDS},
	isbn = {0020-1669},
	url = {<Go to ISI>://000222165700043},
	author = {Jones, N. D. and Foo, S. J. L. and Patrick, B. O. and James, Brian R.}
}
