Formation and reactivity of the zirconium ethylene complexes [η5-C5H3-1,3-(SiMe2CH2PR2)2]Zr(η2-CH2=CH2)(X) (R = Me, Pr i; X = Br, C5H5)

2001 ◽  
Vol 79 (5-6) ◽  
pp. 536-545 ◽  
Author(s):  
Michael D Fryzuk ◽  
Paul B Duval ◽  
Steven J Rettig
Keyword(s):  
Carbon Monoxide ◽  
Solid State ◽  
Kinetic Parameters ◽  
Structure Determination ◽  
Exchange Process ◽  
Carbonyl Complex ◽  
Carbonyl Ligand ◽  
Minor Isomer ◽  
X Ray ◽  
X Ray Crystallography

The formation and reactivity of the zirconium ethylene complexes R[P2Cp]Zr(η2-CH2=CH2)(X) (2a: R = Pri, X = Br; 2b: R = Me, X = Br; 4a: R = Pri, X = C5H5; R[P2Cp] = (η5-C5H3-1,3-(SiMe2CH2PR2)2)) are described. Ethylene complexes 2a and 2b are prepared from a reaction of R[P2Cp]ZrCl3 (1a: R = Pri; 1b: R = Me) with 2 equiv of EtMgBr, presumably via β-H elimination from the diethyl intermediate R[P2Cp]ZrCl(CH2CH3)2. The structure of 2b was determined by X-ray crystallography. Addition of carbon monoxide to 16-electron 2 displaces the ethylene ligand to generate the carbonyl complex R[P2Cp]Zr(CO)2Br (5a: R = Pri; 5b: R = Me), which is stable only under an atmosphere of CO. The corresponding CO reaction with 18-electron 4a to give the metallocene monocarbonyl analogue Pr[P2Cp]Zr(η5-C5H5)(CO) (6a) is considerably slower. 2a exhibits fluxional exchange of one carbonyl ligand with bulk 13CO in solution; the kinetic parameters for this exchange process are ΔH ‡ = 9.2(5) kcal mol–1 and ΔS ‡ = –17(2) cal mol–1 K–1. The addition of diphenylacetylene to 2a yields the alkyne complex Pr[P2Cp]Zr(η2-PhCCPh)Br (7a), which exists in solution as two isomers in equilibrium. A solid-state X-ray structure determination for the minor isomer syn-7a was performed.Key words: zirconium, cyclopentadienyl phosphine, alkyne, metallocyclopropane.

Bis(1-phenyl-1-propyne) complexes of tungsten(II): crystal structures of [WI2(CO)(NCR)(η2-MeC2Ph)2] (R = Me, Et, or Ph)

2001 ◽  
Vol 79 (3) ◽  
pp. 263-271
Author(s):  
Paul K Baker ◽  
Michael GB Drew ◽  
Deborah S Evans
Keyword(s):  
Carbon Monoxide ◽  
Solid State ◽  
Crystal Structures ◽  
Octahedral Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Alkyne Complexes ◽  
First Time

Reaction of [WI2(CO)3(NCMe)2] with two equivalents of 1-phenyl-1-propyne (MeC2Ph) in CH2Cl2, and in the absence of light, gave the bis(1-phenyl-1-propyne) complex [WI2(CO)(NCMe)(η2-MeC2Ph)2] (1) in 77% yield. Treatment of equimolar quantities of 1 and NCR (R = Et, i-Pr, t-Bu, Ph) in CH2Cl2 afforded the nitrile-exchanged products, [WI2(CO)(NCR)(η2-MeC2Ph)2] (2-5) (R = Et (2), i-Pr (3), t-Bu (4), Ph (5)). Complexes 1, 2, and 5 were structurally characterized by X-ray crystallography. All three structures have the same pseudo-octahedral geometry, with the equatorial sites being occupied by cis and parallel alkyne groups, which are trans to the cis-iodo groups. The trans carbon monoxide and acetonitrile ligands occupy the axial sites. In structures 1 and 2, the methyl and phenyl substituents of the 1-phenyl-1-propyne ligands are cis to each other, whereas for the bulkier NCPh complex (5), the methyl and phenyl groups are trans to one another. This is the first time that this arrangement has been observed in the solid state in bis(alkyne) complexes of this type.Key words: bis(1-phenyl-1-propyne), carbonyl, nitrile, diiodo, tungsten(II), crystal structures.

Solid-State NMR and X-Ray Crystallography: Complementary Tools for Structure Determination

1988 ◽  
Vol 1 (4) ◽  
pp. 281-333 ◽  
Author(s):  
Margaret C. Etter ◽  
Rebecca C. Hoye ◽  
Gail M. Vojta
Keyword(s):  
Solid State ◽  
Structure Determination ◽  
Solid State Nmr ◽  
X Ray ◽  
X Ray Crystallography

scholarly journals A Mixed-metal Mixed-halide Complex Prepared from Zerovalent Copper and Lead Salts: Solution and Solid-state Chemistry

1999 ◽  
Vol 23 (11) ◽  
pp. 670-671
Author(s):  
Larisa A. Kovbasyuk ◽  
Olga Yu. Vassilyeva ◽  
Vladimir N. Kokozay ◽  
Wolfgang Linert ◽  
Paul R. Raithby
Keyword(s):  
Solid State ◽  
Direct Interaction ◽  
Solid State Chemistry ◽  
X Ray ◽  
Mixed Metal ◽  
X Ray Crystallography ◽  
Halide Complex ◽  
Layer Arrangement ◽  
Lead Salts

The mixed-metal mixed-halide complex [CuPbBrlL2]2 has been prepared by the direct interaction of zerovalent copper with lead halides and 2-dimethylaminoethanol (HL) in dmso and has been characterized by X-ray crystallography; the structure shows a layer arrangement of the tetranuclear metal units through the μ3-halogen bridging.

Synthesis and structural characterization of a magnesium phthalocyanine(3–) anion

2012 ◽  
Vol 16 (01) ◽  
pp. 154-162 ◽  
Author(s):  
Edwin W.Y. Wong ◽  
Daniel B. Leznoff
Keyword(s):  
Absorption Spectrum ◽  
Solid State ◽  
Single Crystal ◽  
Structural Characterization ◽  
Heterometallic Complex ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.

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