title: Synthesis, characterization, and hydrolytic behavior of mixed-ligand diorganotin esters, [R2Sn(O2CR')OSO2Me]2 (R=n-Pr, n-Bu; R'=C9H6N-2, 4-OMe-C9H5N-2, C9H6N-1).
abstract: Reactions of the tin precursors, R2Sn(OMe)OSO2Me (R=n-Pr, n-Bu), with an equimolar quantity of 2-quinoline/4-methoxy-2-quinoline/1-isoquinoline carboxylic acid in acetonitrile proceed under mild conditions (rt,12-15 h) via selective Sn-OMe bond cleavage to afford the corresponding mixed-ligand diorganotin derivatives [R2Sn(O2CR')OSO2Me]2 [R'=C9H6N-2, R=n-Pr (1), n-Bu (2); R'=4-OMe-C9H5N-2, R=n-Pr (3), n-Bu (4); R'=C9H6N-1, R=n-Pr (5), n-Bu (6)]. These have been characterized by FAB mass, IR, and multinuclear (1H, 13C, 119Sn) NMR spectral data and X-ray crystallography (for 4 and 6). The molecular structure of 4 (C20H29NO6SSn, monoclinic, P2(1)/n, a=14.1(13) A, b=16.7(18) A, c=20.3(19) A, beta=107(4) degrees, Z=8) comprises distorted octahedral geometry around each tin atom by virtue of weakly bridging methanesulfonate [Sn(1A)-O(3B)=3.010, Sn(1B)-O(3A)=2.984 A] and (N,O) chelation of the carboxylate ligands. The spectral data of 1-4 suggest a similar structural motif in solution. The molecular structure of 6 (C38H53N2O10S2Sn2, monoclinic, P2(1)/c, a=11.339(2) A, b=14.806(3) A, c=24.929(5) A, beta=100.537(3) degrees, Z=4) reveals varying bonding preferences with monomeric units being held together by a bridging methanesulfonate [Sn(2)-O(5)=2.312(2) A] and a carboxylate group bonded to Sn(1) and Sn(2) atoms, respectively. Slow hydrolysis of compound 2 derived from 2-quinoline carboxylic acid in moist CH3CN affords the asymmetric distannoxane, [Bu2Sn(O2CC9H6N-2)-O-Sn(OSO2Me)Bu2]2 (7) (C27H45NO6SSn2, monoclinic, C2/c, a=21.152(3) A, b=13.307(2) A, c=26.060(4) A, beta=110.02(10) degrees, Z=8) featuring ladder type structural motif by virtue of unique mu2-coordination of covalently bonded oxygen atoms [O(6), O(6)#1] of the methanesulfonate groups.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India. shankar@netearth.iitd.ac.in
authors.forename: Ravi
authors.initials: R
authors.lastname: Shankar
authors.forename: Mukesh
authors.initials: M
authors.lastname: Kumar
authors.forename: Raj K
authors.initials: RK
authors.lastname: Chadha
authors.forename: Geeta
authors.initials: G
authors.lastname: Hundal