Insertion reactions of hydridonitrosyltetrakis(trimethylphosphine) tungsten(0)

Dalton Transactions Pub Date: 2005-01-05 DOI: 10.1039/B414943B

Abstract

[W(H)(NO)(PMe3)4] (1) was prepared by the reaction of [W(Cl)(NO)(PMe3)4] with NaBH4 in the presence of PMe3. The insertion of acetophenone, benzophenone and acetone into the W–H bond of 1 afforded the corresponding alkoxide complexes [W(NO)(PMe3)4(OCHR1R2)] (R1 = R2 = Me (2); R1 = Me, R2 = Ph (3); R1 = R2 = Ph (4)), which were however thermally unstable. Insertion of CO2 into the W–H bond of 1 yields the formato-O complex trans-W(NO)(OCHO)(PMe3)4 (5). Reaction of trans-W(NO)(H)(PMe3)4 with CO led to the formation of mer-W(CO)(NO)(H)(PMe3)3 (6) and not the formyl complex W(NO)(CHO)(PMe3)4. Insertion of Fe(CO)5, Re2(CO)10 and Mn2(CO)10 into trans-W(NO)(H)(PMe3)4 resulted in the formation of trans-W(NO)(PMe3)4(μ-OCH)Fe(CO)4 (7), trans-W(NO)(PMe3)4(μ-OCH)Re2(CO)9 (8) and trans-W(NO)(PMe3)4(μ-OCH)Mn2(CO)9 (9). For Re2(CO)10, an equilibrium was established and the thermodynamic data of the equilibrium reaction have been determined by a variable-temperature NMR experiments (K298 K = 104 L mol?1, ΔH = ?37 kJ mol?1, ΔS = ?86 J K?1 mol?1). Both compounds 7 and 8 were separated in analytically pure form. Complex 9 decomposed slowly into some yet unidentified compounds at room temperature. Insertion of imines into the W–H bond of 1 was also additionally studied. For the reactions of the imines PhCH[double bond, length as m-dash]NPh, Ph(Me)C[double bond, length as m-dash]NPh, C6H5CH[double bond, length as m-dash]NCH2C6H5, and (C6H5)2C[double bond, length as m-dash]NH with 1 only decomposition products were observed. However, the insertion of C10H7N[double bond, length as m-dash]CHC6H5 into the W–H bond of 1 led to loss of one PMe3 ligand and at the same time a strong agostic interaction (C17–H?W), which was followed by an oxidative addition of the C–H bond to the tungsten center giving the complex [W(NO)(H)(PMe3)3(C10H6NCH2Ph)] (10). The structures of compounds 1, 4, 7, 8 and 10 were studied by single-crystal X-ray diffraction.

Graphical abstract: Insertion reactions of hydridonitrosyltetrakis(trimethylphosphine) tungsten(0)
Recommended Literature