Phosphaniminato-Komplexe des Zinks mit Hydrido-, Alkinylo-, Alkenylo- und Amido-Liganden

Krieger, Matthias; Gould, Robert O.; Neumüller, Bernhard; Harms, Klaus; Dehnicke, Kurt

doi:10.1002/(sici)1521-3749(199809)624:9<1434::aid-zaac1434>3.0.co;2-7

Cited by 29 publications

(15 citation statements)

References 5 publications

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“…Wright et al synthesized the first zinc acetylide derivatives in 1996, [17] and Dehnicke et al have prepared a number of zinc acetylide derivatives. [18,19] Monomeric compounds with three-coordinate zinc are still quite rare; only a few examples have been reported in the literature. [20Ϫ27] Here we report on the formation of a monomeric zinc acetylide complex with a three-coordinate zinc atom.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characterization of β-Diketoiminate Complexes Containing Three-Coordinate Zinc and Copper Atoms

Prust

Hohmeister

Stasch

et al. 2002

Eur. J. Inorg. Chem.

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Keywords: Acetylides / Copper / N ligands / ZincThe reaction of the lithium β-diketoiminate complex (dipp)NacNacLi·OEt 2 {(dipp)NacNac = 2-[(2,6-diisopropylphenyl)amino]-4-[(2,6-diisopropylphenyl)imino]pent-2-enyl} with ZnCl 2 yielded the corresponding (dipp)NacNacZnCl (1) and (dipp)NacNacZn(µ-Cl) 2 Li(OEt 2 ) 2 (1a). Treatment of 1 with LiCϵCPh and NaBH 4 in diethyl ether gave (dipp)NacNacZnCϵCPh (2) and (dipp)NacNacZn(µ-H) 2 BH 2 (3). The core element of compounds 1a−3 is a six-membered ZnN 2 C 3 ring. The structure of 1a shows the β-diketoiminate backbone in a boat conformation with the tetrahedrally coordinated metal centre in 1a at the prow and the opposing carbon atom at the stern. The zinc atoms in 2 and 3 show a planar

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Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characterization of β-Diketoiminate Complexes Containing Three-Coordinate Zinc and Copper Atoms

Prust

Hohmeister

Stasch

et al. 2002

Eur. J. Inorg. Chem.

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“…The alkynylimido group is linear at C6 (178.9(5)°) and C7 (178.5(4)°) and has a C6C7 bond length of 1.205(5) Å, all of which are typical for alkynes. The C sp Si bond length of 1.816(4) Å is similar to those in trimethylsilylalkynes,14b, 15 while the C6N1 bond length of 1.356(5) Å is close to that of 1.344(3) Å in the aminoalkyne C 12 H 8 NCCCCNC 12 H 8 16…”

Section: Methodsmentioning

confidence: 59%

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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“…The molecular structure of 45 was confirmed by single-crystal X-ray diffraction analysis, which revealed that the geometry of central metal is distorted trigonal planar with the shortest Zn-N distance (1.974(2) Å) reported so far. [127][128][129] All the Zn complexes (44)(45)(46) were employed for catalytic hydroboration of different aliphatic and aromatic organic nitriles, and 44 amongst all was found most active in the series (scheme 27). All the complexes displayed excellent tolerance for hydroboration of various electron-deficient and electron-rich organic nitriles and achieved desired diborylamine products within 12h-24h.…”

Section: Scheme 7 Copolymerization Of Ethylene/nbe Bymentioning

confidence: 99%