| 19317408 |
Ganesamoorthy C, Balakrishna MS, Mague JT: Group 11 metal chemistry of a tetradentate ligand, phenylene-1,4-diaminotetra (phosphonite), p-C6H4 [N{P (OC6H4OMe-o) 2}2] 2. Inorg Chem. 2009 Apr 20;48(8):3768-82.
The Cu (I), Ag (I), and Au (I) chemistry of a tetradentate ligand (phenylene-1,4-diaminotetra (phosphonite), p-C (6) H (4)[N{P (OC (6) H (4) OMe-o)(2)}(2)](2) (P (2) NPhiNP (2)) (1)) is described. The flexional conformations in 1 leads to interesting structural variations in transition-metal complexes. The reaction of 1 with 4 equiv of CuX (where X = Br and I) produce the tetranuclear complexes, [{Cu (2)(mu-X)(2)(NCCH (3))(2)}(2)(mu-P (2) NPhiNP (2))] (where X = Br (2) or X = I (3)) in quantitative yield. Treatment of 3 with an excess of pyridine, 2-(piperazin-1-yl) pyrimidine, and pyrazole yielded the tetra-substituted derivatives, [{Cu (2)(mu-I)(2)(L)(2)}(2)(mu-P (2) NPhiNP (2))] (where L = pyridine (4), 2-(piperazin-1-yl) pyrimidine (5), or pyrazole (6)). Similar reactions of 3 with 1,10-phenanthroline (phen) and 2,2'-bipyridine in a 1:2 molar ratio afford the disubstituted derivatives, [(Cu (2)(mu-I))(2) I (2)(phen)(2)(mu-P (2) NPhiNP (2))] (7) and [(Cu (2)(mu-I))(2) I (2)(bipy)(2)(mu-P (2) NPhiNP (2))] (8). The o-methoxyphenoxy substituents on phosphorus in complexes 5 and 7 adopt approximately parallel planar conformations and contain lattice solvents. The reaction of 3 with 1,4-diazabicyclo [2.2.2] octane (DABCO) in a 1:2 molar ratio in a dichloromethane-acetonitrile mixture leads to the formation of an ionic complex [N (CH (2) CH (2))(3) N (+) CH (2) Cl](2)[(Cu (2)(Cl)(I)(2))(2)(NCCH (3))(2)(mu-P (2) N PhiNP (2))](2-) (9), as a result of the chloromethylation of DABCO. Treatment of 1 with 4 equiv of AgClO (4) produces [{Ag (2)(mu-ClO (4))(2))(2)(C (4) H (8) O)(2)}(2)(mu-P (2) NPhiNP (2))] (10). Displacement of perchlorate ions in 10 by PhN{P (OC (6) H (4) OMe-o)(2)}(2) (PNP) or 2,2'-bipyridine yielded [(mu-PNP)(2) Ag (2)(mu-P (2) NPhiNP (2)) Ag (2)(mu-PNP)(2)](ClO (4))(4) (11) and [{Ag (2)(bipy)(2)}(2)(mu-P (2) NPhiNP (2))](ClO (4))(4) (12), respectively. The similar reaction of 1 with 2 equiv of AgOTf, in the presence of 4,4'-bipyridine, gave a three-dimensional Ag (I) coordination polymer, [{Ag (2)(C (10) H (8) N (2))(2)(CH (3) CN)(2)}(2)(P (2) NPhiNP (2))](n)(OTf)(4n) (13). The reactions of 1 with [AuCl (SMe (2))], in appropriate ratios, afford the tetranuclear and dinuclear complexes, [(Au (2) Cl (2))(2)(mu-P (2) NPhiNP (2))] (14) and [(AuCl)(2)(P (2) NPhiNP (2))] (15). Complex 14 undergoes moisture-assisted P-N bond cleavage in the presence of PhN{P (OC (6) H (4) OMe-o)(2)}(2) to give [p-NH (2) C (6) H (4) N{P (OC (6) H (4) OMe-o)(2)}(2) Au (2) Cl (2)] (17) and [PhN{P (OC (6) H (4) OMe-o)(2)}(2) Au (2) Cl (2)]. The structures of the complexes 5, 7-10, 12-15, and 17 are confirmed by single-crystal X-ray diffraction studies. |
1(0,0,0,1) |