Addition of stannylene [{(SiMe3)2CH}2Sn:] (2) to the unbridged homobimetallic Ni–Ni bond of [{PEt3Ni(η5-Cp)}2] (1) gives the heterobimetallic, tetranuclear compound [{{(SiMe3)2CH}2Sn–Ni(η5-Cp)}2] (3) with a butterfly arrangement and leaves the Ni–Ni bond of 1 intact. Elimination of both PEt3 ligands from the starting material 1 is observed, probably due to steric restraints. Compound 3 is formally related to the hypothetical closo-borane B4H42–. The Ni–Ni bond in 3 is only slightly elongated [2.454(3) Å] when compared to the starting material 1 [2.41(1) Å]. Compound 3 displays a butterfly arrangement with a hinge angle of 62.5°. An alternative route to 3 is by a direct reaction between nickelocene (5) and Lappert's stannylene [{(SiMe3)2CH}2Sn:] in 63% yield. Treating 3 with water results in the cleavage of an Ni–Sn bond and subsequent opening of the cluster cage of 3 to form the trinuclear compound [(η5-Cp)Ni{Sn(CH(SiMe3)2}2OH] (6) having an Sn–OH–Sn bridge. The hydroxy proton in 6 can be exchanged by deuterium within a few minutes, as determined by 1H-NMR spectroscopy, giving the monodeuterio product, [D1]-6. Compound 6 is reactive towards acetonitrile, leading to cleavage of one Ni–Sn bond, elimination of one [{(SiMe3)2CH}2Sn:] unit, and formation of the organotin hydroxo complex [{(SiMe3)2CH}2(OH)Sn–Ni(η5-Cp)(CH3CN)] (7). In this complex, acetonitrile is coordinated to Ni via its σ lone pair, bearing the OH ligand in a terminal bonding mode to tin.

Schneider, J.J., Hagen, J., Blaser, D., Boese, R., Fabrizi de Biani, F., Zanello, P., et al. (1999). Synthesis, structure, electrochemistry and reactivity of the bis(mu-sigma-stannanediyl)dinickel butterfly cluster [{{(SiMe3)(2)CH}(2)Sn-Ni(eta(5)-Cp)}(2)](Ni-2-Sn-2). EUROPEAN JOURNAL OF INORGANIC CHEMISTRY(11), 1987-1993 [10.1002/(SICI)1099-0682(199911)1999:11<1987::AID-EJIC1987>3.0.CO;2-4].

Synthesis, structure, electrochemistry and reactivity of the bis(mu-sigma-stannanediyl)dinickel butterfly cluster [{{(SiMe3)(2)CH}(2)Sn-Ni(eta(5)-Cp)}(2)](Ni-2-Sn-2)

Fabrizi de Biani F.;Zanello P.;
1999-01-01

Abstract

Addition of stannylene [{(SiMe3)2CH}2Sn:] (2) to the unbridged homobimetallic Ni–Ni bond of [{PEt3Ni(η5-Cp)}2] (1) gives the heterobimetallic, tetranuclear compound [{{(SiMe3)2CH}2Sn–Ni(η5-Cp)}2] (3) with a butterfly arrangement and leaves the Ni–Ni bond of 1 intact. Elimination of both PEt3 ligands from the starting material 1 is observed, probably due to steric restraints. Compound 3 is formally related to the hypothetical closo-borane B4H42–. The Ni–Ni bond in 3 is only slightly elongated [2.454(3) Å] when compared to the starting material 1 [2.41(1) Å]. Compound 3 displays a butterfly arrangement with a hinge angle of 62.5°. An alternative route to 3 is by a direct reaction between nickelocene (5) and Lappert's stannylene [{(SiMe3)2CH}2Sn:] in 63% yield. Treating 3 with water results in the cleavage of an Ni–Sn bond and subsequent opening of the cluster cage of 3 to form the trinuclear compound [(η5-Cp)Ni{Sn(CH(SiMe3)2}2OH] (6) having an Sn–OH–Sn bridge. The hydroxy proton in 6 can be exchanged by deuterium within a few minutes, as determined by 1H-NMR spectroscopy, giving the monodeuterio product, [D1]-6. Compound 6 is reactive towards acetonitrile, leading to cleavage of one Ni–Sn bond, elimination of one [{(SiMe3)2CH}2Sn:] unit, and formation of the organotin hydroxo complex [{(SiMe3)2CH}2(OH)Sn–Ni(η5-Cp)(CH3CN)] (7). In this complex, acetonitrile is coordinated to Ni via its σ lone pair, bearing the OH ligand in a terminal bonding mode to tin.
1999
Schneider, J.J., Hagen, J., Blaser, D., Boese, R., Fabrizi de Biani, F., Zanello, P., et al. (1999). Synthesis, structure, electrochemistry and reactivity of the bis(mu-sigma-stannanediyl)dinickel butterfly cluster [{{(SiMe3)(2)CH}(2)Sn-Ni(eta(5)-Cp)}(2)](Ni-2-Sn-2). EUROPEAN JOURNAL OF INORGANIC CHEMISTRY(11), 1987-1993 [10.1002/(SICI)1099-0682(199911)1999:11<1987::AID-EJIC1987>3.0.CO;2-4].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11365/22899