Unsaturated Ru(0) Species with a Constrained Bis-Phosphine Ligand: [Ru(CO)2(tBu2PCH2CH2PtBu2)]2. Comparison to [Ru(CO)2(PtBu2Me)2]

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Abstract
The synthesis of Ru(C2H4)(CO)2(dtbpe) (dtbpe = tBu2PC2H4PtBu2), then green [Ru(CO)2(dtbpe)]n is described. In solution, n = 1, while in the solid state, n = 2; the dimer has two carbonyl bridges. DFTPW91, MP2, and CCSD(T) calculations show that the potential energy surface for bending one carbonyl out of the RuP2C(O) plane is essentially flat. Ru(CO)2(dtbpe) reacts rapidly in benzene solution to oxidatively add the H−E bond of H2, HCl, HCCR (R = H, Ph), [HOEt2]BF4, and HSiEt3. The H−C bond of C6HF5 oxidatively adds at 80 °C. CO adds, as does the CC bond of H2CCHX (X = H, F, Me). The following do not add: N2, THF, acetone, H3COH, and H2O.

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