Insertion reactions of hydridonitrosyltetrakis(trimethylphosphine) tungsten(0)

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)( OCHR1 R-2)] ( R-1 = R-2 = Me ( 2); R-1 = Me, R-2 = Ph ( 3); R-1 = R-2 = 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), Re-2( CO) (10) and Mn-2( CO) (10) into trans - W( NO) ( H) ( PMe3) (4) resulted in the formation of trans - W( NO) ( PMe3) (4)( mu - OCH) Fe( CO) (4) ( 7), trans - W( NO) ( PMe3) (4)( mu - OCH) Re-2( CO) (9) ( 8) and trans - W( NO) ( PMe3) (4)( mu - OCH) Mn-2( CO) (9) ( 9). For Re-2( CO)(10), an equilibrium was established and the thermodynamic data of the equilibrium reaction have been determined by a variable- temperature NMR experiments ( K (298 K) = 104 L mol(-1), DeltaH = -37 kJ mol(-1), DeltaS = -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 = NPh, Ph( Me) C = NPh, C6H5CH = NCH2C6H5, and( C6H5) C-2 = NH with 1 only decomposition products were observed. However, the insertion of C10H7N = 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.