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.
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