Saturday, April 07, 2012

Ni, Pd, Pt, and Ru Complexes of Phosphine-Borate Ligands

Abstract Image
Paulina Levario

The species Cy2PHC6F4BF(C6F5)2 reacts with Pt(PPh3)4 to yield the new product cis-(PPh3)2PtH(Cy2PC6F4BF(C6F5)2) 1 via oxidative addition of the P–H bond of the phosphonium borate to Pt(0). The corresponding reaction with Pd(PPh3)4 affords the Pd analogue of 1, namely, cis-(PPh3)2PdH(Cy2PC6F4BF(C6F5)2) 3; while modification of the phosphonium borate gave the salt [(PPh3)3PtH][(tBu2PC6F4BF(C6F5)2)] 2. Alternatively initial deprotonation of the phosphonium borate gave [tBu3PH][Cy2PC6F4BF(C6F5)2] 4, [SIMesH][Cy2PC6F4BF(C6F5)2] 5which reacted with NiCl2(DME) yielding [BaseH]2[trans-Cl2Ni(Cy2PC6F4BF(C6F5)2)2] (Base =tBu3P 6, SIMes 7) or with PdCl2(PhCN)2 to give [BaseH]2[trans-Cl2Pd(Cy2PC6F4BF(C6F5)2)2] (Base = tBu3P 8, SIMes 9). While [C10H6N2(Me)4H][tBu2PC6F4BF(C6F5)2] 10 was also prepared. A third strategy for formation of a metal complex of anionic phosphine-borate derivatives was demonstrated in the reaction of (COD)PtMe2 with the neutral phosphine-borane Mes2PC6F4B(C6F5)2 affording (COD)PtMe(Mes2PC6F4BMe(C6F5)2) 11. Extension of this reactivity to tBu2PH(CH2)4OB(C6F5)3) was demonstrated in the reaction with Pt(PPh3)4 which yieldedcis-(PPh3)2PtH(tBu2P(CH2)4OB(C6F5)3) 12, while the reaction of [SIMesH][tBu2P(CH2)4OB(C6F5)3] 13 with NiCl2(DME) and PdCl2(PhCN)2 afforded the complexes [SIMesH]2[trans-Cl2Ni(tBu2PC4H8OB(C6F5)3)2] 14 and [SIMesH]2[trans-PdCl2(tBu2P(CH2)4OB(C6F5)3)2] 15, respectively, analogous to those prepared with 4 and 5. Finally, the reaction of 7 and 13with [(p-cymene)RuCl2]2 proceeds to give the new orange products [SIMesH][(p-cymene)RuCl2(Cy2PC6F4BF(C6F5)2)] 16 and [SIMesH][(p-cymene)RuCl2(tBu2P(CH2)4OB(C6F5)3)] 17, respectively. Crystal structures of 1, 6, 10, 11, 12, and 16 are reported.

For more information:

Ni, Pd, Pt, and Ru Complexes of Phosphine-Borate Ligands

Stephanie L. Granville, Gregory C. Welch, and Douglas W. Stephan
Inorganic Chemistry Article ASAP
Department of Chemistry, University of Toronto, 80 St. George St. Toronto, Ontario, Canada M5S 3H6
DOI: 10.1021/ic2026895
Publication Date (Web): March 29, 2012
Copyright © 2012 American Chemical Society

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