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

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] 5 which 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 yielded cis-(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 13 with [(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.