| Abstract
| - In [Li(o-C6H4PPh2NSiMe3)]2·Et2O the deprotonated ortho phenyl carbon atom leads to metal−carbon σ bonds in reactions with metal halides and the Ph2PNSiMe3 moiety donates an electron pair to that metal via the imine nitrogen atom. Only two of the three sidearms present donate in the sterically crowded [In(o-C6H4PPh2NSiMe3)3] complex, while both nitrogen atoms coordinate the iron(II) in the 14-VE complex [Fe(o-C6H4PPh2NSiMe3)2]. In [Ph3Ge(o-C6H4PPh2NSiMe3)] the Ge···N distance is too long to account for a highly coordinated germanium center.
- Lithiation of triphenyl((trimethylsilyl)imino)phosphorane, Ph3PNSiMe3 (1), with MeLigives the ortho-metalated species [Li(o-C6H4PPh2NSiMe3)]2·Et2O (2). It has all the requirements of an organometallic ligand capable of sidearm donation: the deprotonated orthophenyl carbon atom leads to metal−carbon σ bonds in reactions with metal halides, and thePh2PNSiMe3 moiety donates an electron pair to that metal via the imine nitrogen atom.In reactions with InCl3 the In(III) organometallic complex [In(o-C6H4PPh2NSiMe3)3] (3) wasobtained, while with FeCl2 a new example of the rare iron(II) 14-VE complexes [Fe(o-C6H4PPh2NSiMe3)2] (4) was obtained. Reaction of 2 with Ph3GeCl gave [Ph3Ge(o-C6H4PPh2NSiMe3)] (5). While in 4 both imino sidearms coordinate to the metal, because of stericcrowding only two of the three present coordinate in 3. Because of the low Lewis acidity ofthe tetraorganogermanium moiety the imino sidearm does not donate to the centralgermanium atom in 5.
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