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Bi-, tetra-, and hexanuclear au-i and binuclear ag-i complexes and ag-i coordination polymers containing phenylaminobis(phosphonite), phn{p(oc6h4ome-o)(2)}(2), and pyridyl ligands

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Title Bi-, tetra-, and hexanuclear au-i and binuclear ag-i complexes and ag-i coordination polymers containing phenylaminobis(phosphonite), phn{p(oc6h4ome-o)(2)}(2), and pyridyl ligands
 
Creator GANESAMOORTHY, C
BALAKRISHNA, MS
MAGUE, JT
TUONONEN, HM
 
Subject nuclear magnetic-resonance
gold(i) thiolate complexes
closed-shell interactions
ray crystal-structure
molecular-structures
structural-characterization
spectroscopic properties
photophysical properties
copper(i) complexes
phosphine complexes
 
Description The reactions of phenylaminobis(phosphonite), PhN{P(OC6H40Me-P)(2))}(2) (1) (PNP), with [AuCl(SMe2)] in appropriate ratios, afford the bi- and mononuclear complexes, [(AuCl)(2)(U-PNP)] (2) and [(AuCl)(PNP)](2) (3) in good yield. Treatment of 2 with 2 equiv of AgX (X = OTf or ClO4) followed by the addition of 1 or 2,2'-bipyridine affords [Au-2(mu-PNP)(2)](OTf)(2) (4) and [Au-2(C10H8N2)(2)(mu-PNP)](ClO4)(2) (5), respectively. Similarly, the macrocycles [Au-4(C4H4N2)(2)(mu-PNP)(2)](ClO4)(4) (6), [Au-4(C10H8N2)(2)(mu-PNP)(2)](ClO4)(4) (7), and [Au-6(C3H3N3)(2)(mu-PNP)(3)](ClO4)(6) (8) are obtained by treating 2 with pyrazine, 4,4'-bipyridine, or 1,3,5-triazine in the presence of AgClO4. The reaction of 1 with AgOTf in a 1:2 molar ratio produces [Ag-2(mu-OTf)(2)(mu-PNP)) (9). The displacement of triflate ions in 9 by 1 leads to a disubstituted derivative, [Ag-2(mu-PNP)(3)](OTf)(2) (10). The equimolar reaction of 1 with AgClO4 in THF affords [Ag-2(C4H80)(2)(mu-PNP)(2)](ClO4)(2) (11). Treatment of 1 with AgClO4 followed by the addition of 2,2'-bipyridine affords a discrete binuclear complex, [Ag-2(C10H8N2)(2)(mu-PNP)](ClO4)(2) (12), whereas similar reactions with 4,4'-bipyridine or pyrazine produce one-dimensional zigzag Ag' coordination polymers, [Ag-2(C10H8N2)(mu-ClO4)(ClO4)(mu-PNP)](n) (13) and [Ag-2(C4H4N2)(mu-ClO4)(ClO4)(mu-PNP)](n) (14) in good yield. The nature of metal-metal interactions in compounds 2, 4, 5, and 12 was analyzed theoretically by performing HF and CC calculations. The structures of the complexes 2, 4, 5, 7, 9, 12, and 14 are confirmed by single crystal X-ray diffraction studies.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-10-14T12:10:17Z
2011-12-15T09:16:21Z
2011-10-14T12:10:17Z
2011-12-15T09:16:21Z
2008
 
Type Review
 
Identifier INORGANIC CHEMISTRY,47(7)2764-2776
0020-1669
http://dx.doi.org/10.1021/ic702133f
http://dspace.library.iitb.ac.in/xmlui/handle/10054/13918
http://hdl.handle.net/100/3122
 
Language en