Cadmium and Mercury Complexes Containing Trinuclear Titanium Imido‐Nitrido Metalloligands

Abstract

Several heterometallic nitrido complexes have been prepared from the reaction of the trinuclear imido‐nitrido titanium complex [{Ti(η5‐C5Me5)(μ‐NH)}3(μ3‐N)] (1) with cadmium and mercury derivatives. Treatment of 1 with cadmium dichloride or cadmium diiodide in toluene afforded the adducts [X2Cd{(μ3‐NH)3Ti3(η5‐C5Me5)3(μ3‐N)}] [X = Cl (2), I (3)]. Complex 2 reacted with lithium reagents [LiR] in toluene to give the cube‐type derivatives [RCd{(μ3‐N)(μ3‐NH)2Ti3(η5‐C5Me5)3(μ3‐N)}] [R = CH2SiMe3 (4), C≡CSiMe3 (5), C5H4(SiMe3) (6), N(SiMe3)2 (7)]. The amido complex 7 reacted with 1 equiv. of 1 to give the corner‐shared double‐cube complex [Cd{(μ3‐N)(μ3‐NH)2Ti3(η5‐C5Me5)3(μ3‐N)}2] (8) by means of bis(trimethylsilyl)amine elimination. Treatment of 1 with mercury(II) iodide in toluene gave the adduct [I2Hg{(μ3‐NH)3Ti3(η5‐C5Me5)3(μ3‐N)}] (9), which reacted with [K{N(SiMe3)2}] to afford [Hg{(μ3‐N)2Ti3(η5‐C5Me5)3(μ‐NH)(μ3‐N)}]2 (10) through the amido mercury intermediate [{(Me3Si)2N}Hg{(μ3‐N)Ti3(η5‐C5Me5)3(μ‐NH)2(μ3‐N)}] (11). Compound 11 and the analogous alkyl derivative [(Me3SiCH2)Hg{(μ3‐N)Ti3(η5‐C5Me5)3(μ‐NH)2(μ3‐N)}] (12) were characterised by NMR spectroscopy upon the treatment of 1 with [Hg{N(SiMe3)2}R] [R = N(SiMe3)2, CH2SiMe3]. Complex [Hg{(μ3‐N)Ti3(η5‐C5Me5)3(μ‐NH)2(μ3‐N)}2] (13), with one bridging mercury atom between two titanium trinuclear systems, was obtained upon treatment of HgI2 with the potassium derivative [K(μ4‐N)(μ3‐NH)2{Ti3(η5‐C5Me5)3(μ3‐N)}]2. Complexes 3, 5 and 8 were characterised by single‐crystal X‐ray diffraction analysis.

Heterometallic Cube‐Type Molecular Nitrides

“…[88] Group ). [93] The X-ray crystal structure of the [Hg2{(3-N)2Ti3Cp*3(-NH)(3-N)}2] shows two linear mercury atoms bridging two incomplete cube [Ti3N4] units. [88] An analogous compound [Hg{(3- from the original report.…”

Zinc, cadmium and mercury

“…41 Zinc complexes of the [(Z 6 -C 6 H 5 CO 2 )Cr(CO) 3 ] À ligand have also been reported. 42 The trinuclear imido-nitrido titanium complex [{Ti(Z 5 -C 5 Me 5 )(m-NH)} 3 (m 3 -N)] has been shown to form adducts with CdX 2 (X = Cl, I); 43 Potentially 'energetic' complexes based on 4-amino-1,2,4-triazole (4-ATZ) have been described viz. [Cd(4-ATZ) 2 (Ac) 2 (H 2 O)] and [Cd(4-ATZ) 2 (H 2 O) 2 ](picrate) 2 .…”

“…47 A Cu/Hg mixed-metal network has been described, based on Hg(CN) 2 and Cu(N 3 ) 2 (py) 2 fragments that associate via long 'secondary' Hg-N 3 bonds, 48 while a less ambiguous Cu/Hg bimetallic has been obtained with a sulfur-rich macrocycle (10), the dimercury complex of which has also been described. 49 The complex [I 2 Hg{(m 3 -NH) 3 Ti 3 (Z 5 -C 5 Me 5 ) 3 (m 3 -N)}] has been obtained analogously to its cadmium congener (vide supra); in contrast to the latter, 43 The organometallic chemistry of mercury has been somewhat more prolific. This has included the synthesis of the trimetallic 11, derived from a tricarbene ligand 50 and the application of the 'oxide route' to prepare the NHC complexes [{C 3 (NAr) 2 }HgX 2 ] (Ar = C 6 H 3 -2,6-i Pr 2 , Mes; X = Cl, I) from the respective imidazolium halide, HgO and [NBu 4 ]X.…”

Dispersion Makes a Difference – The Solid‐State Structure of Hg[N(SiMe3)2]2

“…It was synthesized by a metathesis reaction of NaN(SiMe 3 ) 2 with HgBr 2 (Scheme ). Since then, compound 1 has found widespread use, for example, as a starting material for the synthesis of mercury–chalcogene compounds,, earth alkali silyl amides, organomercury compounds, in transition metal complexes and cyclisation reactions …”