The crystal structure of (1) has been determined by X-ray crystallographic methods. The compound crystallises in the monoclinic space group C2/c with a= 14.002(6), b= 13.059(7), c= 19.158(8)A, β= 96.00(3)°, and Z= 4. The [WOCl3(PPh3O)2] molecule is disordered over two orientations in the crystal and possesses a crystallographically imposed C2 axis passing through the W atom. The disordered atoms are Cl(2) and O(2). Molecular dimensions are W–Cl(1), 2.369(4); W–O(1), 2.088(11); W–Cl(2), 2.242(10); and W–O(2), 2.053(22)A. Single-crystal e.s.r. spectra of (1) diluted in the niobium analogue gave g1= 1.739 ± 0.002, g2= 1.763 ± 0.002, and g3= 1.770 ± 0.002, whilst a similar study on [AsPh4][WOCl4(OH2)] gave g∥= 1.806 ± 0.001 and g⊥= 1.765 ± 0.001. The e.s.r. data for [WOCl3(PPh3O)2], [MoOCl3(PPh3O)2], and [MoOCl3{P(NMe2)3O}2] are discussed in terms of an angular-overlap model for their electronic structures.

Chemischer InformationsdienstVolume 11, Issue 46 Physical Organic Chemistry ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE OF TRICHLOROOXOBIS(TRIPHENYLPHOSPHINE OXIDE)TUNGSTEN(V), (1). SINGLE CRYSTAL ELECTRON SPIN RESONANCE SPECTRA OF (1) AND TETRAPHENYLARSONIUM AQUATETRACHLOROOXOTUNGSTATE(V) AND ELECTRONIC STRUCTURES OF THESE AND SOME RELATED MOLYBDENUM(V) COMPOUNDS L. H. HILL, L. H. HILLSearch for more papers by this authorN. C. HOWLADER, N. C. HOWLADERSearch for more papers by this authorF. E. MABBS, F. E. MABBSSearch for more papers by this authorM. B. HURSTHOUSE, M. B. HURSTHOUSESearch for more papers by this authorK. M. A. MALIK, K. M. A. MALIKSearch for more papers by this author L. H. HILL, L. H. HILLSearch for more papers by this authorN. C. HOWLADER, N. C. HOWLADERSearch for more papers by this authorF. E. MABBS, F. E. MABBSSearch for more papers by this authorM. B. HURSTHOUSE, M. B. HURSTHOUSESearch for more papers by this authorK. M. A. MALIK, K. M. A. MALIKSearch for more papers by this author First published: November 18, 1980 https://doi.org/10.1002/chin.198046076AboutPDF 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. Volume11, Issue46November 18, 1980 RelatedInformation

Crystals of the title complex are tetragonal, space group P4/n, with a= 12.590(7), c= 7.840(5)Å, and Z= 2. The crystal structure has been solved by the heavy-atom method and refined by full-matrix least-squares calculations to R 0.059 over 860 statistically signrfrcant reflections from diffractometer measurements (Cu-Kα radiation). The square-pyramidal [CrCl4O]– anion has crystallographic 4mm(C4v) symmetry with Cr–O 1.519(12) and Cr–Cl 2.240(3)Å, and O–Cr–Cl 104.5(1)°. The [AsPh4]+ cation has crystallographic (S4) symmetry [As–C 1.906(6)Å C–As–C 105.3(3) and 111.5(3)°]. E.s r. spectroscopy has been used to estimate the equilibrium constants for the reaction [CrCl4O]–+ L [graphic omitted] [CrCl4OL]n– in CH2Cl2solution {n= 1 when L = PPh3O (K= 3 ± 2), P(NMe2)3O (K= 463 ± 130), thf (K < 1), or py (K= 160); n= 2 when L = Cl–(K= 43 ± 10 with [AsPh4]Cl and 250 ± 33 dm3 mol–1 with [NEt4]Cl)}.

Chemischer InformationsdienstVolume 8, Issue 29 Physical Organic Chemistry ChemInform Abstract: CRYSTAL AND MOLECULAR STRUCTURE, ELECTRON SPIN RESONANCE, AND ELECTRONIC SPECTRUM OF TETRAPHENYLARSONIUM TETRACHLORO-OXOMOLYBDENUM(V) C. D. GARNER, C. D. GARNERSearch for more papers by this authorL. H. HILL, L. H. HILLSearch for more papers by this authorF. E. MABBS, F. E. MABBSSearch for more papers by this authorD. L. MCFADDEN, D. L. MCFADDENSearch for more papers by this authorA. T. MCPHAIL, A. T. MCPHAILSearch for more papers by this author C. D. GARNER, C. D. GARNERSearch for more papers by this authorL. H. HILL, L. H. HILLSearch for more papers by this authorF. E. MABBS, F. E. MABBSSearch for more papers by this authorD. L. MCFADDEN, D. L. MCFADDENSearch for more papers by this authorA. T. MCPHAIL, A. T. MCPHAILSearch for more papers by this author First published: July 19, 1977 https://doi.org/10.1002/chin.197729077AboutPDF 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. Volume8, Issue29July 19, 1977 RelatedInformation

Crystals of the title compound are tetragonal, space group P4/n, with a= 12.766(7), c= 7.785(5)Å, Z= 2. The crystal structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations to R 0.050 over 735 statistically significant reflections from diffractrometer measurements. The square-pyramidal [MoOCl4]– anion has 4mm(C4v) symmetrywith Mo–O 1.610(10), Mo–Cl 2.333(3)Å, O–Mo–Cl 105.2(1)°. The [AsPh4]+ cation has crystallographic (S4) symmetry, with As–C 1.902(7)Å, end C–As–C angles of 105.3(3) and 111.6(3)°. The polarised single-crystal electronic spectra at room temperature and 5 K show that the first two bands at 1 5.4 and 22.5 kK are due to b2*(4dxy)→e*(4dxz,yz, Mo–Oπ*) and e(Mo–Oπ)→a1*(Mo–Oa*) excitation respectively. The single-crystal e.s.r. parameters (g∥ 1.967 ± 0.002, g⊥ 1.950 ± 0.002) and the Mo hyperfine parameters from solutions in CH2Cl2 and solid [AsPh4][NbOCl4], (Ā 47.9 × 10–4 cm–1, A‖ 72.8 × 10–4 cm–1), have been used in conjunction with the electronic spectrum to estimate the metal d-orbital contributions to the metal–ligand antibonding molecular orbitals.