Vanadium Carbonyl Nitrosyl Compounds: The Carbonyl Nitrosyl Chemistry of an Oxophilic Early Transition Metal

Abstract

The vanadium carbonyl nitrosyl compounds V(NO)(CO) n (n = 5, 4, 3) and V 2 (NO) 2 (CO) n (n = 9, 8, 7) have been examined by density functional theory in order to assess the effect of the oxophilicity of vanadium on its metal carbonyl nitrosyl chemistry. The expected octahedral structure for the experimentally known, but surprisingly unstable, V(NO)(CO) 5 , is confirmed by DFT. The optimized structures of the unsaturated derivatives V(NO)(CO) 4 and V(NO)(CO) 3 can be derived from the octahedral V(NO)(CO) 5 structure by loss of one or two carbonyl groups, respectively. This leads to a nearly square-planar predicted structure for V(NO)(CO) 3 . The lowest energy structures for the binuclear derivatives V 2 (NO) 2 -(CO) n (n = 9, 8, 7) have exclusively two-electron donor carb-

Electronic, Conjugation, and Confinement Effects on Structure, Redox, and Catalytic Behavior of Oxido-Vanadium(IV) and -(V) Chiral Schiff Base Complexes

“…In general, electron deficiency and oxophilicity of the V(V) ion are supposed to be the main driving force behind the dimerization process. 31,35 In the present case, such forces persist in case of complexes 3 and 4 while the same was partially nullified in case of complexes 1 and 2 because of the electronic effect imparted by the electron-donating substituent and extended conjugation associated with ligands, L1 and L2, respectively. L. M. Morky and C. J.…”

Binuclear ruthenium carbonyl nitrosyls: Comparison with Fe2(NO)2(CO)n and Rh2(CO)n

“…Our previous DFT studies on the binuclear manganese carbonyl nitrosyls [17] Mn 2 (NO) 2 (CO) n (n = 7, 6, 5, 4) and the binuclear iron carbonyl nitrosyls [13] Fe 2 (NO) 2 (CO) n (n = 7, 6, 5, 4, 3) also indicated a clear energetic preference for structures with bridging NO groups relative to isomeric structures with bridging CO groups. However, a similar DFT study of the binuclear chromium carbonyl nitrosyls Cr 2 (NO) 2 (CO) n (n = 8, 7, 6, 5) [15] and the binuclear vanadium carbonyl nitrosyls V 2 (NO) 2 (CO) n (n = 9, 8, 7) [14] did not indicate a similar energetic preference of bridging NO groups over bridging CO groups. We can conclude that the energetic preference for bridging NO groups over bridging CO groups is a feature of the relatively electron-rich later transition metals.…”

“…The analogous iron carbonyl nitrosyl systems Fe 2 (NO) 2 (CO) n were the subjects of a previous DFT study [13]. In addition, metal carbonyl nitrosyl derivatives of vanadium [14], chromium [15], tungsten [16], manganese [17], and cobalt [18] have been studied by DFT methods.…”

An ab initio investigation of some hydrogen-bonded complexes of methanol and dimethylamine

“…For the (CH 3 ) 2 NH series, reducing the symmetry from C s to C 1 led to the (CH 3 ) 2 NHÁP(CH 3 ) 3 and (CH 3 ) 2 NHÁCH 3 Cl adducts reverting to energy minima, but the complex with CH 3 F still failed to yield a full set of real eigenvalues. The small value of the imaginary wavenumber (18i cm À1 ), however, suggests that this finding is an artifact of the numerical procedure, as has been proposed elsewhere [14]. Some sample optimized structures are illustrated in Fig.…”