Alkyne insertion reactions in nickel acyl complexes. Occurrence of a 1,2-trimethylphosphine shift and the x-ray structures of [cyclic] Ni[C(Ph):C(H)(COCH2SiMe3)]Cl(PMe3)2 and [cyclic] Ni[C(Ph)(PMe3)C(H)(COCH2CMe2Ph)]Cl(PMe3)6

1984 ◽  
Vol 3 (9) ◽  
pp. 1438-1440 ◽  
Author(s):  
Ernesto Carmona ◽  
Enrique Gutierrez-Puebla ◽  
Angela Monge ◽  
Jose M. Marin ◽  
Margarita Paneque ◽  
...  
Keyword(s):  
Insertion Reactions ◽  
X Ray ◽  
Acyl Complexes ◽  
Alkyne Insertion

Insertion reactions of CO2, OCS, and CS2 into the Sn–N bonds of (Me2N)2Sn: NMR and X-ray structural characterization of the products

2011 ◽  
Vol 376 (1) ◽  
pp. 73-79 ◽  
Author(s):  
Constantine A. Stewart ◽  
Diane A. Dickie ◽  
Yongjun Tang ◽  
Richard A. Kemp
Keyword(s):  
Structural Characterization ◽  
Insertion Reactions ◽  
X Ray

scholarly journals Visible light driven generation and alkyne insertion reactions of stable bis-cyclometalated Pt(iv) hydrides

2020 ◽  
Vol 11 (44) ◽  
pp. 12095-12102
Author(s):  
Dionisio Poveda ◽  
Ángela Vivancos ◽  
Delia Bautista ◽  
Pablo González-Herrero
Keyword(s):  
Visible Light ◽  
Addition Reactions ◽  
Insertion Reactions ◽  
Photochemical Generation ◽  
Visible Light Driven ◽  
Alkyne Insertion

The photochemical generation of isolable bis-cyclometalated Pt(iv) hydrides via photooxidative C–H addition reactions is demonstrated from easily accessible Pt(ii) precursors using visible light.

C—br insertion reactions in rhodium and iridium compounds containing an ortho-halo-arylphosphine. X-ray structures of two ortho-metallated compounds of formula IrX2[P(C6F4)Ph2][P(o-BrC6F4)Ph2], (X = Cl, Br)

Polyhedron ◽  
1988 ◽  
Vol 7 (2) ◽  
pp. 87-96 ◽  
Author(s):  
J.Carlos Besteiro ◽  
Pascual Lahuerta ◽  
Mercedes Sanatú ◽  
Isabel Solana ◽  
F.Albert Cotton ◽  
...  
Keyword(s):  
Insertion Reactions ◽  
X Ray

Alkene and Alkyne Insertion Reactions with Tantalum Metallacarborane Complexes:  the Et2C2B4H42-Carborane Ligand as a Spectator and Participant1

1998 ◽  
Vol 17 (18) ◽  
pp. 3865-3874 ◽  
Author(s):  
Eric Boring ◽  
Michal Sabat ◽  
M. G. Finn ◽  
Russell N. Grimes
Keyword(s):  
Insertion Reactions ◽  
Carborane Ligand ◽  
Alkyne Insertion

Silaheterocyclen, XXIV. / Silaheterocycles, XXIV.

1993 ◽  
Vol 48 (3) ◽  
pp. 318-332 ◽  
Author(s):  
Norbert Auner ◽  
Armin W. Weingartner ◽  
Eberhardt Herdtweck
Keyword(s):  
Energy Levels ◽  
Cycloaddition Reaction ◽  
Product Distribution ◽  
Diels Alder ◽  
Frontier Molecular Orbitals ◽  
X Ray Diffraction ◽  
Insertion Reactions ◽  
Ene Reaction ◽  
X Ray ◽  
Cycloaddition Product

The 1-amino-2-neopentylsilenes 5-8 are formed in the reaction of LitBu with the aminovinylsilanes 1-4 in n-pentane (addition of LitBu to the vinylic double bond with subsequent 1,2-elimination of LiCl). The α-Li adducts initially formed are trapped by Me3SiOSO2CF3 to yield α-SiMe3-silanes. The silenes undergo insertion reactions into the Si—O bond of Me3SiOMe. In the absence of any trapping reagent dimerization occurs. One of the 1,3-disilacyclobutanes thus formed (15) could be examined by X-ray diffraction. Reacting with 1,3-butadienes the chlorosubstituted silenes 5 and 8 yield [2 + 2]-cycloaddition products. With 1,3-cyclohexadiene Diels-Alder adducts are also obtained, but with cyclopentadiene the [4+2] adducts are formed exclusively. Products of an ene-reaction are observed upon treatment of 2,5-norbornadiene with the silenes 5 and 8.The methylsubstituted silene 6 does not undergo any cycloaddition reaction at all, while from silene 7 only traces of the cycloadducts are produced. Both species mainly yield the dimers. The preference for the [2+2] reaction type, exhibited by the silenes 5 and 8, is due to their polarity. The almost complete absence or low yield of any cycloaddition products from 6 or 7 can be correlated with the energy levels of their frontier molecular orbitals. The distribution of the disilacyclobutanes and cycloaddition product isomers is explained by the characteristics of the stereospecifically Ε-configurated silenes. The product distribution can also be rationalized considering the ambiphilic nature of the system ViRR′SiCl/Li1Bu.

Unexpected ring opening of cycloaminocarbene complexes of chromium upon alkyne insertion reactions

1988 ◽  
Vol 358 (1-3) ◽  
pp. 245-272 ◽  
Author(s):  
H. Rudler ◽  
A. Parlier ◽  
R. Yefsah ◽  
B. Denise ◽  
J.C. Daran ◽  
...  
Keyword(s):  
Ring Opening ◽  
Insertion Reactions ◽  
Alkyne Insertion

Hydrido(acylenolato)cobalt(III)-Verbindungen mit Trimethylphosphan- Liganden: Insertionsreaktionen mit Alkinen und die ersten Carbonylcobalt(III)-Komplexe / Hydrido(acylenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands: Insertion Reactions with Alkynes and the First Carbonylcobalt(III) Complexes

2000 ◽  
Vol 55 (8) ◽  
pp. 707-717 ◽  
Author(s):  
Hans-Friedrich Klein ◽  
Xiaoyan Li ◽  
Ulrich Flörke ◽  
Hans-Jürgen Haupt
Keyword(s):  
Axial Position ◽  
Coupling Reactions ◽  
Carbonyl Complexes ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
Insertion Reactions ◽  
X Ray ◽  
Reversible Transformation ◽  
Tert Butyl ◽  
Trigonal Bipyramidal

Abstract Formal insertion of phenylethyne into Co-H functions of mer-octahedral acyl(enolato)-cobalt(III) hydrides 1-3 proceeds under ambient conditions affording η1-vinylcobalt(III) compounds where the dianionic acyl(enolato) ligands are derived from 2-formyl-4-phenyl-cyclohexanone (4), 1-formyl-cyclohexan-2-one (5), and 3-hydroxo-2,3-diphenyl-propenal (6). Dissociation and association of trimethylphosphane results in a reversible transformation of penta-coordinate complexes 4 -6 into hexa-coordinate ones 7 -9, respectively, involving different tautomeric vinyl species. In toluene solution 9 rearranges by reductive C,C coupling into a 5,6-η2-olefin(enolato)cobalt(I) complex 10. Trimethylsilylethyne undergoes a hydrolytic desilylation reaction which is followed by reductive C,C-coupling reactions of acyl and vinyl functions selectively producing chelating η1-enolato-5,6-η2-olefin ligands in cobalt(I) com ­ pounds 13 -16 where the (ax,eq)chelating ligands are derived from 1-formyl-cyclohexan-2-one (13), 3-hydroxo-2,3-diphenyl-propenal (14), 2-formyl-α-tetralone (15), and 2-formyl-4-tert-butyl-cyclohexanone (16). An axial position of the enolato-O donor in the trigonal bipyramidal configuration of complex 15 has been confirmed by X-ray diffraction analysis. With 1,4-bis(trimethylsilyl)buta-diyne 1,2-addition in cobalt(III) hydrides 2, 3, 11 (as deriverd from 2-formyl-α-tetralone), and 12 (as derived from 2-formyl-4-tert-butyl-cyclohexanone) produces 2-metalated vinyl groups in compounds 17 -20. Dissociation of trimethylphosphane from 17 and 19 does not activate C,C coupling at the cobalt(III) centre of penta-coordinate 21 and 22. Steric congestion in compounds 17, 18, and 20 favours exchange of trimethylphosphine for carbon monoxide affording the first octahedral carbonyl complexes of cobalt (d6) (23 -25). In the crystal and in solution a meridional configuration is adopted by complex 23 with the CO group in a position opposite to the acyl function.

Sign in / Sign up

Export Citation Format

Share Document