Structural and spectroscopic study of a five-coordinate rhodium(I) complex (η-1,5-cyclooctadiene)(η-2, 6-diallylpyridine,N)rhodium (1+) with two different and unusual di-μ-chloro-bis[dichlorodimethylstannate](2−) anions. Crystal structures of [Rh(C8H12)-(C11H13N)]2[{SnCl3(CH3)2}2] · 2CH2C12 and [Rh(C8H12)-(C11H13N)]2[{SnCl3(CH3)2}2] |
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Authors: | Maurizio Lanfranchi Maria Angela Pellinghelli Giuseppe Vasapollo Cosimo Francesco Nobile |
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Institution: | 1. Istituto di Chimica Generale ed Inorganica, Centro di Studio per la Strutturistica Diffrattometrica del C. N. R., Via M. D'Aieglio 85, 43100, Parma, Italy 2. Dipartimento di Chimica, Centro di Studio sulle Metodologie Innovative di sintesi Organiche del C. N. R. Universita' di Bari, Via G. Amendola 173, 70126, Bari 3. Universita' degli Studi della Basilicata, Via Nazario Sauro 85, 85100, Potenza, Italy
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Abstract: | The preparation and structures of a five-coordinate rhodium(I) complex with 2,6-diallylpyridine (DAP) and cyclooctadiene (COD) ligands with two different {SnCl3(CH3)2}2]2? anions are described, including IR and1H NMR data. The crystals of the title compounds are both triclinic P¯1: C42H62Cl6N2Rh2Sn2·2CH2Cl2 (1)a=12.200(4),b=13.016(4),c=9.402(2) Å,α=93.92(1),β=100.67(1), γ=115.03(2)°,V c =1311.2(7) Å3,Z= 1,R=0.0312 for 3321 independent observed reflections; C42H62Cl6N2Rh2Sn2 (2)a=12.187(3),b=12.851(3),c=7.752(2) Å,α=90.15(1),β=101.22(1), γ=73.29(1)°,V c =1138.8(5) Å3,Z=1,R=0.0429 for 4117 independent observed reflections. In both structures the cationic rhodium has a trigonal-bipyramidal environment with theN-pyridine and one double bond of the COD ligand in axial positions and the two allylic double bonds together with the other double COD bond in equatorial positions. Much more interesting are the structures of the anionic parts, which show a different unsymmetrical dimerization through two chlorine bridges. The tin coordination polyhedra, which assume a distorted trigonal-bipyramidal geometry in the monomeric units, achieve an octahedral shape. There is a simple correlation between the Me-Sn-Me angle value and the longest Sn-Cl bond distance. |
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