Cube-Type Nitrido Complexes Containing Titanium and Zinc/Copper

Martı́n, Avelino; Martínez-Espada, Noelia; Mena, Miguel; Pérez‐Redondo, Adrián; Yélamos, Carlos

doi:10.1021/ic0603407

Cited by 22 publications

(20 citation statements)

References 62 publications

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“…The amido cadmium complex 7 is stable to ambient light in solution in contrast to the behaviour observed for the zinc analogue [{(Me 3 Si) 2 N}Zn{(μ 3 -N)(μ 3 -NH) 2 Ti 3 (η 5 -C 5 Me 5 ) 3 (μ 3 -N)}]. [12] Additionally, this amido zinc derivative did not react with 1 even at high temperatures, while the treatment of the analogous cadmium compound 7 with 1 equiv. of 1 in toluene at room temperature gave 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) (Scheme 2).…”

Section: Cadmium Compoundsmentioning

confidence: 94%

“…The two units are associated by long-range interactions between the cadmium atom of one fragment and the iodine atom I(2) of the other moiety. If this Cd···I interaction is considered, the geometry around the Cd(1) centre can be defined as distorted trigonal-prismatic, with three iodine atoms [I(1), I(2) and I(2)a] located in an eclipsed position with respect to the three imido-nitrogen atoms [N (12), N (13) [14] and could be indicative of the existence of weak hydrogen-bonding interactions. The Cd(1)-I(1) and Cd(1)-I(2) bond lengths [terminal 2.755(2) Å and bridging 2.791(1) Å, respectively] are similar to the values found in other compounds containing μ-I-bridged Cd 2 I 4 units.…”

Section: Cadmium Compoundsmentioning

confidence: 99%

“…These NMR spectroscopic data are consistent with C s symmetry in solution and tetrahedral geometries for the cadmium centres. The [12] and several crystallographically documented cyclopentadienylcadmium derivatives. [18] The X-ray crystal structure of [(Me 3 SiCϵC)Cd{(μ 3 -N)(μ 3 -NH) 2 Table 2.…”

Section: Cadmium Compoundsmentioning

confidence: 99%

“…All hydrogen atoms were included, positioned geometrically and refined by using a riding model. Two imido hydrogen atoms were statistically distributed over the nitrogen atoms N (12) …”

Section: X-ray Crystal Structure Determination Of Complexes 3 5 Andmentioning

confidence: 99%

“…However, once the adducts [(1)ML n ] are formed, the NH imido groups can be deprotonated leading to monoanionic, dianionic or even trianionic forms of 1 depending on the metal and the other ligands present in the coordination sphere. [10b,11] As part of this general study, we have reported the formation of several azaheterometallocubane complexes by the reaction of the metalloligand 1 with zinc(II) reagents, [12] and we present here the results obtained from studies of the treatment of this preorganised system with cadmium and mercury derivatives. Part of the mercury chemistry has been recently communicated.…”

Section: Introductionmentioning

confidence: 99%

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Cadmium and Mercury Complexes Containing Trinuclear Titanium Imido‐Nitrido Metalloligands

et al. 2011

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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.

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Section: Cadmium Compoundsmentioning

confidence: 94%

Section: Cadmium Compoundsmentioning

confidence: 99%

Section: Cadmium Compoundsmentioning

confidence: 99%

“…All hydrogen atoms were included, positioned geometrically and refined by using a riding model. Two imido hydrogen atoms were statistically distributed over the nitrogen atoms N (12) …”

Section: X-ray Crystal Structure Determination Of Complexes 3 5 Andmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cadmium and Mercury Complexes Containing Trinuclear Titanium Imido‐Nitrido Metalloligands

et al. 2011

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Addition of Terminal Alkynes to a Molecular Titanium–Zinc Nitride

et al. 2007

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Dedicated to Professor Gerhard Erker on the occasion of his 60th birthdayTransition-metal nitrido complexes have been studied extensively in the past few decades. [1, 2] While nitrido complexes of Group 6-8 metals usually bear the nitrido ligands as a terminal functionality, M N, [3] the analogous derivatives of early transition metals exhibit polynuclear structures, with m nnitrido ligands bridging two or more metal centers. [2,4,5] The reactivity of terminal nitrido ligands has received increasing attention because of their potential to show either nucleophilic or electrophilic character. [1,3,6] The net result of the latter is usually a two-electron reduction of the metal center and a reduced bond order between the metal and the nitrogen atom [Eq. (1)]. Recently a similar behavior has been pro-posed for the nucleophilic attack of a phosphine to a bridging dinitride species; in that case the reduction leads to a complex with a metal-metal bond.[7]Over the last few years we have been studying the reactivity of the trinuclear imido-nitrido titanium derivative [{Ti(h 5 -C 5 Me 5 )(m-NH)} 3 (m 3 -N)] [8] (1) towards metal complexes and have reported the coordination of 1 to these metals through the imido groups to give the cube-type adducts [1·ML n ].[9] The elimination of organic molecules and the formation of nitrido groups that bridge the metal centers occur if the NÀH bonds of the organometallic ligand 1 are activated by metal-imido, metal-amido, or metal-alkyl linkages.[10] However, none of those processes involves the triply bridging apical nitrido ligand of 1. Herein we present the first example of a reaction at this nitrido ligand, which leads to an alkynylimido ligand by C À N bond formation. We have studied this "apparent" nucleophilic attack of an acetylide at the apical nitrido ligand by density functional calculations and propose a plausible reaction mechanism.Our synthetic route is outlined in Scheme 1. Treatment of the amido zinc derivative 2 [11] with one equivalent of terminal alkyne RCCH in toluene gives the expected zinc acetylides [{(RCC)Zn}(m 3 -N)(m 3 -NH) 2 {Ti(h 5 -C 5 Me 5 )} 3 (m 3 -N)], with R = SiMe 3 (3), CMe 3 (4), or Ph (5), as brown or red solids in good yields (71-87 %). Because of the light sensitivity of 2 in solution, the reactions were performed in amber-stained glassware. Complexes 3 and 4 were obtained at room temperature, while 5 had to be prepared at 90 8C to obtain a pure sample. Reaction of 2 with two equivalents of Me 3 SiCCH led to a complex which was shown by X-ray diffraction to be the zinc acetylide [{(RCC)Zn}(m 3 -NH) 3 {Ti-(h 5 -C 5 Me 5 )} 3 (m 3 -NCCR)], with R = SiMe 3 (6). The analogous reaction with PhCCH gave the complex with R = Ph (7). Both 6 and 7 were obtained as black solids in good yields (81 and 91 %, respectively). In contrast, the reaction of 2 with more than two equivalents of tert-butylacetylene at a variety of temperatures only produced a mixture of 4 and the unreacted alkyne. [D 6 ]Benzene solutions of 6 are stable at different temperatures, wh...

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