Syntheses and structures of alkaline Earth-transition metal bimetallic complexes as heterogeneous hydrodechlorination catalyst precursors.

A series of alkaline earth-transition metal heterobimetallic complexes {(DMF)(x)M(mu-CN)(y)M*(CN)(4-y)}(infinity) [M = Ba: M* = Ni 1, M* = Pd 2, M* = Pt 3; M = Sr: M* = Ni 4, M* = Pd 5, M* = Pt 6; x = 3 or 4; y = 3 or 4] was prepared. Single-crystal X-ray diffraction analysis revealed that {(DMF)(4)Ba(mu-CN)(3)Ni(CN)}(infinity) 1, {(DMF)(4)Sr(mu-CN)(3)Ni(CN)}(infinity) 4, {(DMF)(4)Sr(mu-CN)(3)Pd(CN)}(infinity) 5, and {(DMF)(4)Sr(mu-CN)(3)Pt(CN)}(infinity) 6 form isostructural one-dimensional "ladder" arrays through isocyanide linkages (M-NC-M*), while {(DMF)(3)Ba(mu-CN)(4)Pd}(infinity) 2, and {(DMF)(3)Ba(mu-CN)(4)Pt}(infinity) 3 are two-dimensional puckered sheet like arrays. These bimetallic complexes can serve as effective precursors for the synthesis of supported bimetallic catalysts.

Preparation and crystal structures of a series of titanium(III) 9-BBN hydroborate complexes containing Ti...H agostic interactions.

9-BBN hydroborate complexes Ti{(mu-H)2BC8H14}3(THF)2 (1), Ti{(mu-H)2BC8H14}3(OEt2) (2), and [K(OEt2)4]-[Ti{(mu-H)2BC8H14}4] (4) were formed from the reaction of TiCl4 with K[H2BC8H14] in diethyl ether or THF. Ti{(mu-H)2BC8H14}3(PhNH2) (3) was isolated from the reaction of 2 with aniline in diethyl ether. In the formation of these complexes, Ti(IV) is reduced to Ti(III).

Synthesis and X-ray and neutron structures of Zr{(mu-H)2BC8H14}4.

The complex Zr(9-BBN)4 [9-BBN = (mu-H)2BC8H14] has been synthesized via the reaction of K(9-BBN) with ZrCl4 in diethyl ether. The structure of the title compound has been determined by X-ray and neutron single-crystal diffraction techniques. Each 9-BBN ligand is coordinated to the Zr atom via two B-H-Zr bridges, and these metal-ligand bonding interactions are further augmented by three prominent C-H.

Synthesis, structural characterization, and reactions of cyclic organohydroborate half-zirconocene compounds.

Cyclic organohydroborate complexes of zirconium monocyclopentadienyl CpZr[(mu-H)(2)BC(5)H(10)](3), 1, and CpZr[(mu-H)(2)BC(8)H(14)](3), 2, were prepared from the reaction of CpZrCl(3) with 3 mol of K[H(2)BC(5)H(10)] and K[H(2)BC(8)H(10)], respectively, in diethyl ether. Compounds 1 and 2 react with the hydride ion abstracting agent B(C(6)F(5))(3) to form the same salt [CpZr(OEt)(OEt(2))(mu-OEt)](2)[HB(C(6)F(5))(3)](2), 5. The complexes CpZr(Cl)[(mu-H)(2)BC(8)H(14)](2), 3, and CpZr(Cl)[(mu-H)(2)BC(8)H(14)](2) [where Cp = C(5)(CH(3))(5)], 4, were prepared from the reaction of CpZrCl(3) and CpZrCl(3) with K[H(2)BC(8)H(10)] in 1:2 molar ratios, respectively.