Syntheses and Molecular Structures of [RSn{W(CO)3Cp}2][W(CO)3Cp], [RSn{W(CO)3Cp}Cl2], and [RSn{W(CO)3Cp}Cr(CO)5] (R = [4-t-Bu-2,6{P(O)(OR′)2}2C6H2], R′ = Et, i-Pr). Autoionization Induced by Intramolecular P=O→Sn Coordination

The syntheses of the intramolecularly coordinated organotin-substituted transition metal complexes [RSn{W(CO)(3)Cp}(2)}[W(CO)(3)Cp] (2, R = 4-t-Bu-2,6-{P(O)(Oi-Pr)(2)}(2)C6H2), [RSn{W(CO)(3)Cp}Cl-2] (4, R = 4-t-Bu-2,6-{P(O)(Oi-Pr)(2)}(2)C6H2), and [RSn{W(CO)(3)Cp}Cr(CO)(5)] (5, R = 4-t-Bu-2,6-{P(O)(OEt)(2)}(2)C6H2) are reported. The reaction of compound 2 with Ph4B+Br- gave the benzoxaphosphastannole [1(P),3(Sn)-Sn[W(CO)(3)Cp](2)OP(O)(Oi-Pr)-6-t-Bu-4-P(O)(Oi-Pr)(2)C6H2] (3). The compounds are characterized by H-1, C-13, P-31, Sn-119 NMR and IR spectroscopy and, except for 3, by single crystal X-ray diffraction analysis. The experimental work is accompanied by DFT calculations.