Cadmium and Mercury Complexes Containing Trinuclear Titanium Imido-Nitrido Metalloligands
✍ Scribed by Avelino Martín; Miguel Mena; Adrián Pérez-Redondo; Carlos Yélamos
- Book ID
- 102830615
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 613 KB
- Volume
- 2011
- Category
- Article
- ISSN
- 1434-1948
No coin nor oath required. For personal study only.
✦ Synopsis
Abstract
Several heterometallic nitrido complexes have been prepared from the reaction of the trinuclear imido‐nitrido titanium complex [{Ti(η^5^‐C~5~Me~5~)(μ‐NH)}~3~(μ~3~‐N)] (1) with cadmium and mercury derivatives. Treatment of 1 with cadmium dichloride or cadmium diiodide in toluene afforded the adducts [X~2~Cd{(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}] [X = Cl (2), I (3)]. Complex 2 reacted with lithium reagents [LiR] in toluene to give the cube‐type derivatives [RCd{(μ~3~‐N)(μ~3~‐NH)~2~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}] [R = CH~2~SiMe~3~ (4), C≡CSiMe~3~ (5), C~5~H~4~(SiMe~3~) (6), N(SiMe~3~)~2~ (7)]. The amido complex 7 reacted with 1 equiv. of 1 to give the corner‐shared double‐cube complex [Cd{(μ~3~‐N)(μ~3~‐NH)~2~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}~2~] (8) by means of bis(trimethylsilyl)amine elimination. Treatment of 1 with mercury(II) iodide in toluene gave the adduct [I~2~Hg{(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}] (9), which reacted with [K{N(SiMe~3~)~2~}] to afford [Hg{(μ~3~‐N)~2~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ‐NH)(μ~3~‐N)}]~2~ (10) through the amido mercury intermediate [{(Me~3~Si)~2~N}Hg{(μ~3~‐N)Ti~3~(η^5^‐C~5~Me~5~)~3~(μ‐NH)~2~(μ~3~‐N)}] (11). Compound 11 and the analogous alkyl derivative [(Me~3~SiCH~2~)Hg{(μ~3~‐N)Ti~3~(η^5^‐C~5~Me~5~)~3~(μ‐NH)~2~(μ~3~‐N)}] (12) were characterised by NMR spectroscopy upon the treatment of 1 with [Hg{N(SiMe~3~)~2~}R] [R = N(SiMe~3~)~2~, CH~2~SiMe~3~]. Complex [Hg{(μ~3~‐N)Ti~3~(η^5^‐C~5~Me~5~)~3~(μ‐NH)~2~(μ~3~‐N)}~2~] (13), with one bridging mercury atom between two titanium trinuclear systems, was obtained upon treatment of HgI~2~ with the potassium derivative [K(μ~4~‐N)(μ~3~‐NH)~2~{Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}]~2~. Complexes 3, 5 and 8 were characterised by single‐crystal X‐ray diffraction analysis.