The species Cy2PHC6F4BF(C6F5)(2) reacts with Pt(PPh3)(4) to yield the new product cis-(PPh3)(2)PtH(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)(2)PdH(Cy2PC6F4-BF(C6F5)(2)) 3; while modification of the phosphonium borate gave the salt [(PPh3)(3)-PtH][(tBu(2)PC(6)F(4)BF(C6F5)(2))] 2. Alternatively initial deprotonation of the phosphonium borate gave [tBu(3)PH][Cy2PC6F4BF(C6F5)(2)] 4, [SIMesH] [CY2PC6F4BF(C6F5)(2)] 5 which reacted with NiCl2(DME) yielding [BaseH](2)[trans-Cl2Ni(Cy2PC6F4BF-(C6F5)(2))(2)] (Base = tBu(3)P 6, SIMes 7) or with PdCl2(PhCN)(2) to give [BaseH](2)[trans-Cl2Pd(Cy2PC6F4BF(C6F5)(2))(2)] (Base = tBu(3)P 8, SIMes 9). While [C10H6N2(Me)(4)H][rBu(2)PC(6)F(4)BF(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 Mes(2)PC(6)F(4)B(C6F5)(2) affording (COD)PtMe(Mes(2)PC(6)F(4)BMe(C6F5)(2)) 11. Extension of this reactivity to tBu(2)PH(CH2)(4)OB(C6F5)(3)) was demonstrated in the reaction with Pt(PPh3)(4) which yielded cis-(PPh3)(2)PtH(tBu(2)P(CH2)(4)OB(C6F5)(3)) 12, while the reaction of [SIMesH][tBu(2)-P(CH2)(4)OB(C6F5)(3)] 13 with NiCl2(DME) and PdCl2(PhCN)(2) afforded the complexes [SIMesH](2)[trans-Cl2Ni(tBu(2)PC(4)H(3)OB-(C6F5)(3))(2)] 14 and [SeLmesH](2)[trans-PdCl2(tBu(2)P(CH2)(4)OB(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(tBu(2)P(CH2)(4)OB(C6F5)(3))] 17, respectively. Crystal structures of 1, 6, 10, 11, 12, and 16 are reported.