Toluene Ligand Research Articles

Synthesis and characterization of new carboxylate dimers of ruthenium

A series of Ru2Cl(μ-O2CR)4 [R = C2H5 (I), cyclo-C6H11 (II), C6H5 (III), o-ClC6H4 (IV), o-HOC6H4 (V)] complexes has been synthesized by reaction of Ru2Cl(μ-O2CCH3)4 with the appropriate carboxylic acid. The reaction of these insoluble compounds with AgBF4 in thf gives [Ru2(μ-O2CR)4(thf)2]BF4 (VI)-(X) which are soluble in polar organic solvents. The substitution in these complexes of the thf axial ligands in toluene by OPPh3 or pyridine leads to new adducts of the type [Ru2(μ-O2CR)4L2]BF4 [L = OPPh3 (XI)-(XV), L = py (XVI)-(XIX)] which are not easily accessible by other methods. The compounds have been characterized by elemental analysis, electrical conductance, magnetic susceptibility measurements and spectral data.

ChemInform Abstract: Preparation and Structure of the Compound Mo2(NCS)4(Ph2Ppy)2·2THF·2Toluene (Ph2Ppy: 2‐(diphenylphosphino)pyridine).

AbstractThe title complex (I) is prepared by reaction of a solution containing dimeric Mo trifluoroacetate and Me3SiNCS with the organic ligand in toluene.

The reaction of trichlorooxovanadium(V) with some oxygen donor ligands

The β-diketone complexes of chlorooxovanadium(V) of the type VOCl(dik) 2 (where dik ≡ btfac, bzac and ttfac) were prepared by the reaction of VOCl 3 with the appropriate ligand in dry toluene under anhydrous conditions. VOCl 3·Ph 3PO was also prepared by the reaction of VOCl 3 with Ph 3PO in dichloromethane. These complexes were characterized by analysis, melting point measurements, IR and Raman spectra, nuclear magnetic resonance (NMR), mass spectral studies and X-ray powder diffraction.

ChemInform Abstract: Substitution Kinetics of (Os3(CO)11(NCMe)) and (Os3(CO)10(NCMe)2).

ChemInformVolume 18, Issue 9 Organoelement Compounds ChemInform Abstract: Substitution Kinetics of (Os3(CO)11(NCMe)) and (Os3(CO)10(NCMe)2). K. DAHLINGER, K. DAHLINGER J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this authorA. J. POE, A. J. POE J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this authorP. K. SAYAL, P. K. SAYAL J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this authorV. C. SEKHAR, V. C. SEKHAR J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this author K. DAHLINGER, K. DAHLINGER J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this authorA. J. POE, A. J. POE J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this authorP. K. SAYAL, P. K. SAYAL J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this authorV. C. SEKHAR, V. C. SEKHAR J. Tuzo Wilson Lab., Univ. Toronto, Mississauga, Ont. L5L 1C6, Can.Search for more papers by this author First published: March 3, 1987 https://doi.org/10.1002/chin.198709288Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume18, Issue9March 3, 1987 RelatedInformation

Preparation, characterization and reactions of vanadium(IV) β-diketonate complexes

The β-diketone complexes of vanadium(IV), VO(dik) 2 (where dik ≡; btfac, tfac, ttfac, acac, bzac and bzbz) have been prepared either by the reaction of vanadium pentoxide with the appropriate ligand in toluene under reflux for 24 h or by the reaction of a warm aqueous or ethanolic solution of vanadium sulphate with the ligand. The oxovanadium(IV) complexes react with sulphur oxide dichloride and dibromide and phosphorus pentachloride to form dihalovanadium(IV) diketonate complexes. These compounds have been characterized by elemental analysis, melting point measurements, IR and Raman spectra, magnetic susceptibility measurements, electron spin resonance (ESR) and mass spectral studies and X-ray powder diffraction.

Substitution kinetics of [Os3(CO)11(NCMe)] and [Os3(CO)10(NCMe)2

The kinetics of reactions of [Os3(CO)11(NCMe)] and [Os3(CO)10(NCMe)2] with P- or As-donor ligands in p-xylene or toluene have been studied and shown to be characteristic of reversible dissociative processes. In both cases MeCN is ca.10 times more nucleophilic towards the reactive intermediate than is PPh3. Activation parameters confirm the weakness of the Os–NCMe bonds and suggest that loss of the first MeCN from [Os3(CO)10(NCMe)2] may be a concerted process in which a ‘sideways on’ bridging CO replaces the leaving MeCN. The strength of bridge bonding can be estimated to be 30 kJ mol–1.

Structural studies on osmium carbonyl hydrides XXVII. The heteronuclear rhodium-triosmium cluster (μ-H)3Os3Rh(CO)9(η6-C6H5me)

Abstract The complex (μ-H) 3 Os 3 Rh(CO) 9 (η 6 -C 6 H 5 Me), previously synthesized by Shore and hsu has been subjected to a single-crystal X-ray structural analysis. The complex crystallizes in the centrosymmetric monoclinic space group C 2/ m (No. 12) with a 14.178(2), b 14.683(3), c 10.205(1) A, β 92.89(1)°, V 2121.6(6) A 3 and ϱ(calcd) 3.20 g cm −3 for mol. wt. 1020.78 and Z = 4. Diffraction data were collected with a Syntex P2 1 automated four-circle diffractometer (MO- K α : 2θ 4.0–50.0°) and the structure was solved and refined to R F 3.9% for all 1964 independent reflections ( R F 3.2% for those 1726 data with ¦ F 0 ¦ > 3σ(¦ F 0 ¦). All non-hydrogen atoms were located as were the three hydride ligands which bridge the three OsOs bonds. The η 6 -toluene ligand is bonded to the rhodium atom and is subject to a three-fold disorder; the entire molecule lies about a site of crystallographic C s ( m ) symmetry. The metal—metal distances in the tetrahedral cluster are Os(1)Os(1′) 2.88(1) A, Os(1)Os(2) = Os(1′)Os(2) = 2.888(1) A, Os(1)Rh = Os(1′)Rh = 2.702(1) A and Os(2)Rh 2.703(1) A.

ChemInform Abstract: THE CRYSTAL STRUCTURES OF MOME2(η6‐C6H6)(PPHME2)2 AND MOME2(η6‐C6H5ME)(PPHME2)2

The crystal structure of MoMe2(η6-C6H5)(PPhMe2)2 and MoMe2(η6-C6H5Me)(PPhMe2)2 have been determined from three-dimensional X-ray diffraction data collected by counter methods. The former crystallizes in the monoclinic space group P21/n with a= 8.108(4), b= 24.287(8), c= 11.961(5)A, β= 96.59(4)°, and Z= 4 for Dc= 1.36 g cm–3. The final R value was 0.035 based on 1 271 independent observed reflections. MoMe2(η6-C6H5Me)(PPhMe2)2 crystallizes in the triclinic space group P with a= 9.128(2), b= 9.611 (2), c= 14.842(3)A, α= 105.44(3), β= 93.72(3), γ= 102.47(3)°, and Z= 2 for Dc= 1.35 g cm–3. The R value was 0·019 for 3 586 observed reflections. The presence of the methyl group on the toluene ligand does not appreciably alter the electronic environment of the molybdenum atom. In the toluene derivative the two Mo–C(σ) bonds average 2.291 (5)A. The Mo–C(σ) lengths range from 2.250(2) to 2.344(2)A, and are seen to vary in a pair-wise fashion such that the arene shows a tendency to act as a diene.

The crystal structures of MoMe2(η6-C6H6)(PPhMe2)2and MoMe2(η6-C6H5Me)(PPhMe2)2

The crystal structure of MoMe2(η6-C6H5)(PPhMe2)2 and MoMe2(η6-C6H5Me)(PPhMe2)2 have been determined from three-dimensional X-ray diffraction data collected by counter methods. The former crystallizes in the monoclinic space group P21/n with a= 8.108(4), b= 24.287(8), c= 11.961(5)A, β= 96.59(4)°, and Z= 4 for Dc= 1.36 g cm–3. The final R value was 0.035 based on 1 271 independent observed reflections. MoMe2(η6-C6H5Me)(PPhMe2)2 crystallizes in the triclinic space group P with a= 9.128(2), b= 9.611 (2), c= 14.842(3)A, α= 105.44(3), β= 93.72(3), γ= 102.47(3)°, and Z= 2 for Dc= 1.35 g cm–3. The R value was 0·019 for 3 586 observed reflections. The presence of the methyl group on the toluene ligand does not appreciably alter the electronic environment of the molybdenum atom. In the toluene derivative the two Mo–C(σ) bonds average 2.291 (5)A. The Mo–C(σ) lengths range from 2.250(2) to 2.344(2)A, and are seen to vary in a pair-wise fashion such that the arene shows a tendency to act as a diene.

Synthesis, X-ray crystal structure, and chemistry of the cation [(η-MePh)Mo(µ-SMe)4Mo(η-MePh)]2+; easy D2O–NaOD catalysed H–D exchange of the methyl hydrogens of a η-bonded toluene ligand

Treatment of the new paramagnetic cation [(η-PhMe)Mo(py)3]+(py = pyridine) with methane thiol yields the redox active, diamagnetic cation [(η-PhMe)Mo(µ-SMe)4Mo(η-PhMe)]2+ which undergoes complete deuterium exchange of the toluene methyl hydrogens in D2O–Na3PO4 buffer (pD = 11) at 25 °C and which yields the weakly paramagnetic cation [(MeIm)3 Mo(µ-SMe)3-Mo(MeIm)3]3+(MeIm = 1-methylimidazole) on reaction with zinc amalgam in 1-methylimidazole–acetonitrile solution.