The reactivity of a series of disilazido zirconocene complexes is dominated by the migration of anionic groups (hydrogen, alkyl, halide, OTf) between the zirconium and silicon centers. The direction of these migrations is controlled by the addition of two-electron donors (Lewis bases) or two-electron acceptors (Lewis acids). The cationic nonclassical [Cp2ZrN(SiHMe2)2](+) ([2](+)) is prepared from Cp2Zr{N(SiHMe2)2}H (1) and B(C6F5)3 or [Ph3C][B(C6F5)4], while reactions of B(C6F5)3 and Cp2Zr{N(SiHMe2)2}R (R = Me (3), Et (5), n-C3H7 (7), CH═CHSiMe3 (9)) provide a mixture of [2](+) and [Cp2ZrN(SiHMe2)(SiRMe2)](+). The latter products are formed through B(C6F5)3 abstraction of a β-H and R group migration from Zr to the β-Si center. Related β-hydrogen abstraction and X group migration reactions are observed for Cp2Zr{N(SiHMe2)2}X (X = OTf (11), Cl (13), OMe (15), O-i-C3H7 (16)). Alternatively, addition of DMAP (DMAP = 4-(dimethylamino)pyridine) to [2](+) results in coordination to a Si center and hydrogen migration to zirconium, giving the cationic complex [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}H](+) ([19](+)). Related hydrogen migration occurs from [Cp2ZrN(SiHMe2)(SiMe2OCHMe2)](+) ([18](+)) to give [Cp2Zr{N(SiMe2DMAP)(SiMe2OCHMe2)}H](+) ([22](+)), whereas X group migration is observed upon addition of DMAP to [Cp2ZrN(SiHMe2)(SiMe2X)](+) (X = OTf ([12](+)), Cl ([14](+))) to give [Cp2Zr{N(SiHMe2)(SiMe2DMAP)}X](+) (X = OTf ([26](+)), Cl ([20](+))). The species involved in these transformations are described by resonance structures that suggest β-elimination. Notably, such pathways are previously unknown in early metal amide chemistry. Finally, these migrations facilitate direct Si-H addition to carbonyls, which is proposed to occur through a pathway that previously had been reserved for later transition metal compounds.
A comprehensive analysis of the bonding structure of the disilyl zirconocene amide cation {Cp2Zr[N(SiHMe2)2]}+ is conducted by application of an intrinsic orbital localization method that yields quasi-atomic orbitals (QUAOs). An emphasis is placed on describing a previously characterized three-center two-electron interaction between zirconium, hydrogen, and silicon that presents structural and spectroscopic features similar to that of agostic bonds. Expressions of the first-order density matrix in terms of the QUAOs yields bond orders (BOs), kinetic bond orders (KBOs), and the extent of transfer of charge that are useful to determine the electronic nature of the Zr–H–Si bond. The interactions between the QUAOs demonstrate the importance of vicinal interactions in the stabilization of the molecule. In addition, the evolution of the QUAOs during reactions with Lewis bases reveals the role of the Zr–H–Si interaction in facilitating the reaction.
The origin of bonding in the rare-gas-containing molecules HXeCCH, HXeCCXeH, and HXeOXeH is explored using a quasi-atomic orbital (QUAO) analysis. The QUAOs provide qualitative and quantitative data about bonding through transformations of the density matrix. Bond orders, kinetic bond orders, and the extent of transfer of charge are analyzed. Localized molecular orbitals formed from the QUAOs provide additional insights about the relative polarity of bonds formed by xenon. The analysis suggests significant covalent bonding for Xe-Y (Y = C, O) as well as Xe-H, with both bonds using the same pσ-type orbital on Xe. These covalent interactions are established by substantial charge shifts from Xe to Y as well as to H. Accordingly, a covalent three-center four-electron bond links the atoms H-Xe-Y. On the basis of the analysis, electrostatic interactions do not play a significant role in the Xe-Y or Xe-H bonding.
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