SUCCESSIVE REACTIONS OF RHENIUM ISOCYANIDE COMPLEXES WITH NITROGEN-CONTAINING LIGANDS - ONE-FLASK CONVERSION OF REBR(CO)(4)(CNPH) TO [RE(CO)(3)(NH(2)R)(2)(C(NHPH)(NHR))]BR--)(()

The isocyanide complexes ReBr(CO)(4)(CNR) (1) react with Me(3)NO in CH 2Cl2 to give ReBr(CO)(3)(CNR)(NMe(3)) (2). Treatment of 1 with Me(3)NO in the presence of CH3CN yields the nitrile derivatives ReBr(CO)(3)(C NR)(NCMe) (3). The latter on reaction with two-electron-donor ligands L (L = CO, PPh(3)) give ReBr(CO)(3)(CNR)L. Treatment of 3 with amines in CH2Cl2 leads to the formation of ReBr(CO)(3)(CNR)(NH(2)R') (5). Whe n ReBr(CO)(3)(CNPh)(NCMe) (3a) is treated with excess amines in CH2Cl2 for a prolonged period, the diaminocarbene complexes ReBr(CO)(3)(NH(2 )R){C(NHPh)(NHR)} (6) are formed. The latter then react with a further 1 equiv of amine to afford [Re(CO)(3)(NH(2)R)(2){C(NHPh)(NHR)}]Br-+(- ) (7). A one-flask synthesis of 7 was achieved by the interaction of R eBr(CO)(4)(CNPh) with Me(3)NO in the presence of CH3CN followed by rea ction with the desired amine in CH2Cl2 at ambient temperature. ReBr(CO )(3)(CNPh)(PPh(3)) (4a), ReBr(CO)(3)(NH2Pri){C(NHPh)(NHPri)} (6a), and [Re(CO)(3)(NH2Pri)(2){C(NHPh)(NHPri)}]Br-+(-) (7a) have been characte rized by X-ray structure determination. 4a crystallizes in the triclin ic space group P ($) over bar 1; a = 9.801(4) Angstrom, b = 11.190(5)A ngstrom, c = 13.862(5)Angstrom, alpha = 91.49(3)degrees, beta = 108.19 (3)degrees, gamma = 65.52(3)degrees, V = 1305.1(8)Angstrom(3), Z = 2, R = 3.1%, and R(w) = 3.5%. 6a gives monoclinic crystals, space group P 2(1)/n; a = 9.174(2)Angstrom, b = 19.865(2)Angstrom, c = 12.064(2)Angs trom, beta = 112.264(2)degrees, V = 2034.6(6)Angstrom(3), Z = 4, R = 2 .7%, and R(w) = 3.3%. 7a is monoclinic, space group P2(1)/n; a = 13.22 3(2)Angstrom, b = 10.726(3)Angstrom, c = 20.705(2)Angstrom, beta = 103 .35(1)degrees, V = 2857.3(9)Angstrom(3), Z = 4, R = 4.8%, and R(w) = 5 .0%.