Hydrosilylierung von symmetrisch disubstituierten Alkinen und Butadiinen mit L2Ni(0)-Butadiin-Komplexen [L  Ph3P, (o-Tol-O)3P] als Katalysatoren

Tillack, Annegret; Pulst, Siegmar; Baumann, Wolfgang; Baudisch, H.; Kortus, K.; Rosenthal, Uwe

doi:10.1016/s0022-328x(96)06734-4

Cited by 51 publications

(20 citation statements)

References 13 publications

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“…The hydrosilylation of alkynes may be catalyzed by a number of different metal complexes, including rhodium, [5][6][7] iridium, [6,8] ruthenium [9,10] and platinum. [11][12][13] Complexes of the less precious metals nickel, [14] cobalt, [15] and titanium [16] have also [a] Leiden Institute of Chemistry, Leiden University, P. O. Box 9502, 2300 RA Leiden, The Netherlands Fax: +31-71-5274761 E-mail: bouwman@chem.leidenuniv.nl of the symmetric alkyne 3-hexyne in 60 min at 50°C, with 5 mol-% catalyst loading.…”

Section: Introductionmentioning

confidence: 99%

[NiX₂(NHC)₂] Complexes in the Hydrosilylation of Internal Alkynes

et al. 2011

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A number of nickel(II) dihalide complexes with small monodentate N-heterocyclic carbene ligands was synthesized and tested for their catalytic activity in the hydrosilylation of internal alkynes. The nickel(0) active species was obtained from the starting nickel(II) complex by reduction with diethylzinc. In all cases the catalytic reaction yielded the syn product selectively. The fastest catalysts reached full conversion

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Section: Introductionmentioning

confidence: 99%

[NiX₂(NHC)₂] Complexes in the Hydrosilylation of Internal Alkynes

et al. 2011

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“…Related Ni(0) complexes of silylated alkynes have been studied before [25,26,27,28,29,30,31,32,33] mainly for spectroscopic analysis but also with respect to bond activating properties [27,34].…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic and Structural Study of Some Oligosilanylalkyne Complexes of Cobalt, Molybdenum and Nickel

2019

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Metal induced stabilization of α-carbocations is well known for cobalt- and molybdenum complexed propargyl cations. The same principle also allows access to reactivity enhancement of metal coordinated halo- and hydrosilylalkynes. In a previous study, we have shown that coordination of oligosilanylalkynes to the dicobalthexacarbonyl fragment induces striking reactivity to the oligosilanyl part. The current paper extends this set of oligosilanylalkyne complexes to a number of new dicobalthexacarbonyl complexes but also to 1,2-bis(cyclopentadienyl)tetracarbonyldimolybdenum and (dippe)Ni complexes. NMR-Spectroscopic and crystallographic analysis of the obtained complexes clearly show that the dimetallic cobalt and molybdenum complexes cause rehybridization of the alkyne carbon atoms to sp3, while in the nickel complexes one π-bond of the alkyne is retained. For the dicobalt and dimolybdenum complexes, strongly deshielded 29Si NMR resonances of the attached silicon atoms indicate enhanced reactivity, whereas the 29Si NMR shifts of the respective nickel complexes are similar to that of respective vinylsilanes.

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“…The synthetic procedure was quite enigmatic, and the silane was used in high excess with no equimolar reagent ratios tested (Table 4). 164,171,172 A recent publication from our group details the application of commercially available catalysts: Pt 2 (dvs) 3 194, Pt(PPh 3 ) 4 225, or PtO 2 226 in the hydrosilylation of various symmetrical 1,4disubstituted buta-1,3-diynes (1a, 13c, 65a, 227a-b) with sterically and electronically different triethyl-207a and triphenylsilane 195e. Comprehensive optimisation studies were carried out to find the most suitable conditions that permitted obtaining either the monosilylated enynes or bissilyated dienes with high stereo-and regioselectivity.…”

Section: Hydrosilylation Of Conjugated 13-diynes Towards Molecular and Macromolecular Unsaturated Organosilicon Compoundsmentioning

confidence: 99%