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Pnictogen-based vanadacyclobutadiene complexes
Mehrafshan G Jafari1, John B Russell1, Hwan Myung2,3
1Department of Chemistry, University of Pennsylvania Philadelphia Pennsylvania 19104 USA mindiola@sas.upenn.edu.
Abstract:
The reactivity of the V[triple bond, length as m-dash]C Bu multiple bonds in the complex (dBDI)V[triple bond, length as m-dash]C Bu(OEt2) (C) (dBDI2- = ArNC(CH3)CHC(CH2)NAr, Ar = 2,6- Pr2C6H3) with unsaturated substrates such as N[triple bond, length as m-dash]CR (R = Ad or Ph) and P[triple bond, length as m-dash]CAd leads to the formation of rare 3d transition metal compounds featuring α-aza-vanadacyclobutadiene, (dBDI)V(κ2- , - BuCC(R)N) (R = Ad, 1; R = Ph, 2) and β-phospha-vanadacyclobutadiene moieties, (dBDI)V(κ2- , - BuCPCAd) (3). Complexes 1-3 are characterized using multinuclear and multidimensional NMR spectroscopy, including the preparation of the 50% 15N-enriched isotopologue (dBDI)V(κ2- , - BuCC(Ad)15N) (1-15N). Solid-state structural analysis is used to determine the dominant resonance structures of these unique pnictogen-based vanadacyclobutadienes. A systematic comparison with the known vanadacyclobutadiene (dBDI)V(κ2- , - BuCC(H)C Bu) (4) is also presented. Theoretical investigations into the electronic structure of 2-4 highlight the crucial role of unique V-heteroatom interactions in stabilizing the vanadacyclobutadienes and identify the most dominant resonance structures.
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