Abstract
The tetravalent germanium and tin compounds of the general formulae Ph*EX3 (Ph* = C(6)H(3)Trip-2,6, Trip = C(6)H(2)iPr(3)-2,4,6; E = Sn, X = Cl (1a), Br (1b); E = Ge, X = Cl (2)) are synthesized by reaction of Ph*Li center dot OEt2 with EX4. The subsequent reaction of 1a,b with LiP(SiMe3)(2) leads to Ph*EP(SiMe3)(2) (E = Sn (3), Ge (4)) and the diphosphane (Me3Si)(2)PP(SiMe3)(2) by a redox ...
Abstract
The tetravalent germanium and tin compounds of the general formulae Ph*EX3 (Ph* = C(6)H(3)Trip-2,6, Trip = C(6)H(2)iPr(3)-2,4,6; E = Sn, X = Cl (1a), Br (1b); E = Ge, X = Cl (2)) are synthesized by reaction of Ph*Li center dot OEt2 with EX4. The subsequent reaction of 1a,b with LiP(SiMe3)(2) leads to Ph*EP(SiMe3)(2) (E = Sn (3), Ge (4)) and the diphosphane (Me3Si)(2)PP(SiMe3)(2) by a redox reaction. In an alternative approach 3 and 4 are synthesized by using the corresponding divalent compounds Ph*ECl (E = Ge, Sn) in the reaction with LiP(SiMe3)(2). The reactivity of Ph*SnCl is extensively investigated to give with LiP(H)Trip a tin(II)-phosphane derivative Ph*SnP(H)Trip (6) and with Li(2)PIrip a proposed product [Ph*SnPTrip](-) (7) with multiple bonding between tin and phosphorus. The latter feature is confirmed by DFT calculations on a model compound [PhSnPPh](-). The reaction with Li[H2PW(CO)(5)] gives the oxo-bridged tin compound [Ph*Sn {W(CO)(5)}(mu-O)(2)SnPh*] (8) as the only isolable product. However, the existence of 8 as the bis-hydroxo derivative [Ph*Sn{W(CO)(5)}(mu-OH)(2)SnPh* (8a) is also possible. The Sn-IV derivatives Ph*Sn(OSiMe3)(2)Cl (9) and [Ph*Sn(mu-O)Cl](2) (10) are obtained by the oxidation of Ph*SnCl with bis(trimethylsilyl)peroxide and with Me3NO, respectively. Besides the spectroscopic characterization of the isolated products compounds la, 2, 3, 4, 8, and 10 are additionally characterized by X-ray diffraction analysis.
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