Synthesis and Structural Characterization of Heterobimetallic Bismuth Complexes with Main Group and Transition Metals

Abstract

The heterobimetallic bismuth-oxo-bridged complexes containing the Bi−O−M (M = Al, Ga, Ge, Zr, Hf) core were prepared. The reaction of L1BiNMe2 (1) [L1 = 1,8-C10H6(NSiMe3)2] with LM(Me)(OH) and LGe(OH) (M = Al, Ga, L = CH((CMe)NAr)2, Ar = 2,6-iPr2C6H3) proceeds via HNMe2 elimination and provides the complexes L1Bi(μ-O)MMeL (M = Al 2; Ga, 3) and L1Bi(μ-O)GeL (4). The transition metal hydroxides Cp*2ZrMe(OH) and Cp*2HfCl(OH) react with 1 in n-hexane and toluene, respectively, under elimination of 1 equiv of HNMe2 to generate the corresponding complexes L1Bi(μ-O)ZrMeCp*2 (5) and L1Bi(μ-O)HfClCp*2 (6). Compounds 3, 4, and 6 represent the first examples of structurally characterized heterobimetallic complexes featuring the Bi−O−Ga, Bi−O−Ge, and Bi−O−Hf moiety, respectively. The crystal structural data show that the complexes 3 and 4 crystallize in the monoclinic space group P21/c and P21/n, while the complexes 5 and 6 are present in the monoclinic space group Pn. Moreover all compounds have been characterized by element analysis, electron impact mass spectrometry, and NMR spectroscopy.

Preparation of Organometallic Hydroxides and their Reactions with Lanthanide Compounds

“…Compound 16 is soluble in n ‐hexane, toluene, ether, tetrahydrofurane, and dichloromethane. The corresponding compound Cp* 2 HfCl(OH) ( 17 ) was only prepared in situ using Cp* 2 HfCl 2 and equivalent amounts of water (Scheme ) 17.…”

Synthesis and structure of new compounds with Pt–Ga bonds: Insertion of the bulky gallium (I) bisimidinate Ga(DDP) into Pt–Cl bond

“…The eCHe protons of isopropyl groups appear as broad resonances at 2.84 and 3.84 ppm. In addition to the DDP ligand, the resonance associated with methyl protons of GaeCH 3 appears at d; À0.46 ppm in 1 H NMR and that of the methyl carbon resonates at d; À13.8 ppm in 13 C NMR spectrum [5,25,26].…”

1,8‐Bis(borylamido)naphthalene Complexes of Lithium and Zinc(II) Including a Zinc(II) Isocyanide Adduct

“…There are many amido ligand variations known with different types of R and R′ substituents on the nitrogen atoms. Combining the amido functionality with naphthalene backbone as in 1,8‐bis(silylamido)naphthalene ligands (e.g., 1 , Figure ) is one such possibility. It is a useful strategy to make the donor arrangement structurally rigid and to create an effective metal ion chelator.…”