Heavy metalla vinyl-cations show metal-Lewis acid cooperativity in reaction with small molecules (NH3, N2H4, H2O, H2)

Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe3)(3)] [E = Ge (1), Sn (2)] and [Ar*E(Cl)IrH(PMe3)(3)] gives the salts [TbbEIrH(PMe3)(3)][BAr4F] [E = Ge (3), Sn (4)] and [Ar*EIrH(PMe3)(3)][BAr4F] [E = Ge (3 & PRIME;), E = Sn (4 & PRIME;)] (Tbb = 2,6-[CH(SiMe3)(2)](2)-4-(t-Bu)C6H2, Ar* = 2,6-Trip(2)C(6)H(3), Trip = 2,4,6-triisopropylphenyl). Bonding analysis suggests their most suitable description as metalla-tetrela vinyl cations with an Ir E double bond and a near linear coordination at the Ge/Sn atoms. Cationic complexes 3 and 4 oxidatively add NH3, N2H4, H2O, HCl, and H-2 selectively to give: [TbbGe(NH2)IrH2(PMe3)(3)][BAr4F] (5), [TbbE(NHNH2)IrH2(PMe3)(3)][BAr4F] [E = Ge (7), Sn (8)], [TbbE(OH)IrH2(PMe3)(3)][BAr4F] [E = Ge (9), Sn (10)], [TbbE(Cl)IrH2(PMe3)(3)][BAr4F] [E = Ge (11a), Sn (12a)], [TbbGe(H)IrH2(PMe3)(3)][BAr4F] (13), [TbbSn(mu-H-3)Ir(PMe3)(3)][BAr4F] (14), and [TbbSn(H)IrH2(PMe3)(3)][BAr4F] (15). 14 isomerizes to give 15via an 1,2-H shift reaction. Hydride addition to cation 3 gives a mixture of products [TbbGeHIrH(PMe3)(3)] (16) and [TbbGeIrH(2)(PMe3)(3)] (17) and a reversible 1,2-H shift between 16 and 17 was studied. In the tin case 4 the dihydride [TbbSnIrH(2)(PMe3)(3)] (18) was isolated exclusively. The PMe3 and PEt3 derivatives, 18 and [TbbSnIrH(2)(PEt3)(3)] (19), respectively, could also be synthesized in reaction of [TbbSnH(2)](-) with the respective chloride [(R3P)(n)IrCl] (R = Me, n = 4; R = Et, n = 3). Reaction of complex 19 with CO gives the substitution product [TbbSnIrH(2)(CO)(PEt3)(2)] (20). Further reaction with CO results in hydrogen transfer from the iridium to the tin atom to give [TbbSnH(2)Ir(CO)(2)(PEt3)(2)] (21). The reversibility of this ligand induced reductive elimination transferring 20 to 21 is shown.