Differing Reactivities of (trimpsi)M(CO)<sub>2</sub>(NO) Complexes [M = V, Nb, Ta; trimpsi = <i><sup>t</sup></i><sup></sup>BuSi(CH<sub>2</sub>PMe<sub>2</sub>)<sub>3</sub>] with Halogens and Halogen Sources
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Treatment of (trimpsi)V(CO)2(NO) (trimpsi = tBuSi(CH2PMe2)3) with 1 equiv of PhICl2 or C2Cl6 or 2 equiv of AgCl affords (trimpsi)V(NO)Cl2 (1) in moderate yields. Likewise, (trimpsi)V(NO)Br2 (2) and (trimpsi)V(NO)I2 (3) are formed by the reactions of (trimpsi)V(CO)2(NO) with Br2 and I2, respectively. The complexes (trimpsi)M(NO)I2(PMe3) (M = Nb, 4; Ta, 5) can be isolated in moderate to low yields when the (trimpsi)M(CO)2(NO) compounds are sequentially treated with 1 equiv of I2 and excess PMe3. The reaction of (trimpsi)V(CO)2(NO) with 2 equiv of ClNO forms 1 in low yield, but the reactions of (trimpsi)M(CO)2(NO) (M = Nb, Ta) with 1 equiv of ClNO generate (trimpsi)M(NO)2Cl (M = Nb, 6; Ta, 7). Complexes 6 and 7 are thermally unstable and decompose quickly at room temperature; consequently, they have been characterized solely by IR and 31P{1H} NMR spectroscopies. All other new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1·3CH2Cl2, 4·(3/4)CH2Cl2, and 5·THF have been established by single-crystal X-ray diffraction analyses. A convenient method of generating Cl15NO has also been developed during the course of these investigations.
