Bipy, phen, and P(C6H4CH2NMe2-2)3 in the synthesis of cationic silver(I) complexes;: the solid-state structures of [P(C6H4CH2NMe2-2)3]AgOTf and [Ag(phen)2]OTf

The reaction of [P(C6H4CH2NMe2-2)(3)]AgX (1a, X = OTf, 1b, X = OClO3) with equimolar amounts of (LL)-L-boolean AND (2a, (LL)-L-boolean AND = 2,2'-bipyridine, bipy; 2b, (LL)-L-boolean AND = 4,4'-dimethyl-2,2'-bipyridine, bipy'; 2c, (LL)-L-boolean AND = 1,10-phenanthroline, phen) leads to the formation of the cationic complexes {[P(C6H4CH2NMe2-2)(3)]Ag((LL)-L-boolean AND)}X-+(-) = bipy: 3a, X = OTf, 3b, X = ClO4; (LL)-L-boolean AND = bipy': 3c, X = OTf, 3d, X = ClO4; ((LL)-L-boolean AND = phen: 3e, X = OTf, 3f, X = ClO4) in which the building blocks (LL)-L-boolean AND and P(C6H4CH2NMe2-2)(3) act as bidentate chelating ligands and are datively-bound to the silver atom. Spectroscopic studies reveal that on the NMR time-scale the phosphane group is dynamic with exchanging the respective Me2NCH2 built-in arms. While complex 3e is stable in the solid-state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work-up of the reaction mixture allows the isolation of the phosphane P(C6H4CH2NMe2-2)(3) (5) along with [Ag(phen)(2)]OTf (4). The solid-state structures of neutral la and cationic 4 are reported. Mononuclear la crystallizes in the monoclinic space group P2(1)/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10) Angstrom, beta = 106.1260(10), V = 6063.83(11) Angstrom(3) and Z = 4 with 8132 observed unique reflections (R-1 = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3) Angstrom, beta = 113.503(2), V = 4576.8(10) Angstrom(3) and Z = 4 with 6209 observed unique reflections (R-1 = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat-like conformation for the six-membered AgPNCH2C2/phenyl cycles is found. In 4, as typical for 1a, the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63degrees. The OTf group is acting as non-coordinating counter ion.