Not only steric protection by bulky substituents but also intramolecular N→Sn coordination makes possible the isolation and characterization of dimeric organotin(I) compounds such as [{2,6‐(Me2NCH2)2C6H3}Sn]2 (see structure), which according to a crystallographic study exhibits a SnSn bond length of 2.9712(12) Å.
The molecular structures of the intramolecularly coordinated tungstenpentacarbonyl organostannylene complexes 2,6‐(Me2NCH2)2C6H3(Cl)SnW(CO)5 and [2,6‐(Me2NCH2)2C6H3(H2O)SnW(CO)5]+(CB11H12)– are reported. The latter compound is an aqua complex in which the water molecule replaces one of the two N→Sn coordination sites. The coordination of the water molecule is accompanied by proton transfer to the nitrogen atom. DFT calculations reveal this to be the thermodynamically most‐stable structure.
The triorganotin compounds R 2 (NCN)SnX (NCN ) C 6 H 3 (Me 2 NCH 2 ) 2 -2,6 -) containing different polar groups X or substituents R were prepared. The set of organotin compounds Ph 2 (NCN)SnX (X ) I (2), CF 3 CO 2 (3), CH 3 CO 2 (4), Et 2 NCS 2 ( 5)) was prepared to study the influence of the polar group X on the character of the Sn-X bond. The effect of substituents R on the character of the Sn-X bond was studied in two additional sets of organotin compounds, R 2 (NCN)SnCl (R ) Ph ( 6), Bu (7), Me ( 8)) and R 2 (NCN)SnO 2 CCH 3 (R ) Ph (4), Bu (9), Me ( 10)). The influence of different solvents and temperatures on the presence or absence of covalent Sn-X bonds was studied as well. 1 H and 119 Sn NMR spectroscopy showed the occurrence of dissociation of the Sn-O 2 CCH 3 covalent bond in CD 2 Cl 2 solutions of 4, 9, and 10 at various temperatures (range 300-200 K). The crystal structures of 8 and 10 were studied by X-ray crystallography.
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