Preparation and Characterization of a Homoleptic Vanadium(III) Amide Complex and Its Transformation into Terminal Chalcogenide Derivatives [(3,5-Me₂Ph)AdN]₃VE (E = S, Se; Ad = Adamantyl)

Abstract

Reaction of VCl(3)(THF)(3) with (3,5-Me(2)Ph)AdNLi.Et(2)O (Ad = adamantyl) yields the homoleptic vanadium complex [(3,5-Me(2)Ph)AdN](3)V (1), which reacts with chalcogens E (E = S, Se) to yield diamagnetic terminal chalcogenide derivatives [(3,5-Me(2)Ph)AdN](3)V=E [E = S (3a), Se (3b)] Crystal data for 1 and 3a are as follows. 1: C(54)H(72)N(3)V, fw 814.09, triclinic P&onemacr;, a = 10.441(1) Å, b = 11.648(4) Å, c = 19.321(2) Å, alpha = 83.69(2) degrees, beta = 83.89(1) degrees, gamma = 82.42(2) degrees, Z = 2. 3a: C(54)H(72)N(3)VS.(1)/(2)Et(2)O, fw 883.25, monoclinic C2/c, a = 43.400(9) Å, b = 11.744(3) Å, c = 20.705(4) Å, beta = 113.05(1) degrees, Z = 8.

The titanium tris-anilide cation [Ti(N[tBu]Ar)3]+stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4′-bipyridine dititanium complexes

“…8) is the trigonal pyramidal nature of the TiN 3 core unit (the average N-Ti-N angle is ca. 111.3°); despite the presence of two η 3 anilide interactions in the structure of neutral Ti(N[ t Bu]Ar) 3 , 3 the TiN 3 moiety in that case is rigorously trigonal planar, a structural feature common to all of the neutral M(N[R]Ar) 3 complexes that have been characterized to date (M = Ti, 3 V, 25 Cr, 26 Mo 12,[27][28][29] ). Trigonal pyramidal MN 3 units are, however, a characteristic structural feature for homoleptic rare earth metal phenyl(trimethylsilyl) amide complexes.…”

Vanadium nitride functionalization and denitrogenation by carbon disulfide and dioxideElectronic supplementary information (ESI) available: synthetic, spectroscopic, analytical, and computational results for all new complexes. Fig. S1: frontier orbitals of model anions: See http://www.rsc.org/suppdata/cc/b1/b111550m/

“…Surprisingly, storage of a THF solution of 1-NCS 2 Na(THF) 2 at 23 °C for 24 h resulted in complete conversion to 1-S ( 1 H and 51 V NMR), an analogue of the known sulfide 2-S. 4 Removal of solvent in vacuo and dissolution of the remaining red residue in diethyl ether followed by filtration through a fine sintered-glass frit gave, upon drying, dark red microcrystalline 1-S in 94% yield. Collected on the frit was a white salt identified as sodium thiocyanate (96% yield) by comparing its 13 C NMR spectrum in D 2 O with that obtained for a commercially available sample (133.7 ppm).…”

Synthesis of mixed-donor amido/amino/siloxo ligands from symmetrical diamidosilylether ligands via a retro-Brook rearrangement and their chromium(ii) complexes

“…This activation of an arylamido group has been previously observed to a lesser extent in electron-deficient f-element and group 3-5 to transition-metal complexes. 13 Related V(III) and Ti(III) g 3 -amido complexes 14 have been reported but the metrical parameters for the g 2 -(N,C ipso ) arylamido bonding in 7 are by far the shortest and most acute in the literature. Such interactions may help to stabilize the resting state of amido-supported metal complexes that are active in alkene polymerization.…”