dc.contributor.author | Hanna, JV | |
dc.contributor.author | Boyd, SE | |
dc.contributor.author | Healy, PC | |
dc.contributor.author | Bowmaker, GA | |
dc.contributor.author | Skelton, BW | |
dc.contributor.author | White, AH | |
dc.date.accessioned | 2017-05-03T11:10:04Z | |
dc.date.available | 2017-05-03T11:10:04Z | |
dc.date.issued | 2005 | |
dc.date.modified | 2009-08-21T06:38:00Z | |
dc.identifier.issn | 1477-9226 | |
dc.identifier.doi | 10.1039/b505200a | |
dc.identifier.uri | http://hdl.handle.net/10072/4970 | |
dc.description.abstract | The tris(triphenylphosphine)copper(I) complexes [(PPh3)3CuX] for X = Cl (1), Br (2), I (3), ClO4(4), BF4(5), [(PPh3)3CuCl]烈3CN (1a), [Cu(PPh3)3(CH3CN)]X for X = ClO4(6), BF4(7), and [Cu(PPh3)3(CH3CN)]X烈3CN for X = SiF5(8), PF6(9) have been studied by solid state 31P CP/MAS NMR spectroscopy together with single crystal X-ray diffraction for compounds (6)-(9), the latter completing the availability of crystal structure data for the series. Compounds (1)-(5) form an isomorphous series in space group P3 (a 19, c 11 ũ with three independent molecules in the unit cell, all disposed about 3-fold symmetry axes. Average values (with estimated standard deviations) for the P-Cu-P, P-Cu-X bond angles and Cu-P bond lengths in compounds (1)-(3) are 110.1(6)ଠ108.8(6)ࠡnd 2.354(8)Šand 115.2(6)ଠ102.8(9)ࠡnd 2.306(9)Šfor compounds (4) and (5). For the acetonitrile solvated compound (1a), the corresponding parameters are 115(4)ଠ103(3)ࠡnd 2.309(3)Ů The solid state 31P CP/MAS NMR quadrupole distortion parameters, dCu, for (1)-(3) and (1a) are all less than 1 נ109 Hz2, despite the changes in donor properties of the halide in (1)-(3), and the coordination geometry of the P3CuX core in (1a). Change of anion to ClO4- and BF4- in compounds (4) and (5) results in a significant increase of dCu to 4.4-5.2 109 Hz2 and 5.2-6.0 נ109 Hz2, respectively. Compounds (6) and (7) crystallise as isomorphous [Cu(PPh3)3(CH3CN)]X salts in space group Pbca, (a 17.6, b22.3, c24.2 ũ, while compounds (8) and (9) crystallize as isomorphous acetonitrile solvated salts [Cu(PPh3)3(CH3CN)]X烈3CN in space group P(a 10.5, b 13.0, c19.5 Ŭ 104, 104, 94੮ The P3CuN angular geometries in all four compounds are distorted from tetrahedral symmetry with average P-Cu-P, P-Cu-N angles and Cu-P bond lengths of 115(4)ଠ103(4)ࠡnd 2.32(1)Ŭ with dCu ranging between 1.3 and 2.5 נ109 Hz2. The solid state 29Si CP/MAS NMR spectrum of the pentafluorosilicate anion in compound (8) is also reported, affording 1J(29Si, 19F)= 146 Hz. | |
dc.description.peerreviewed | Yes | |
dc.description.publicationstatus | Yes | |
dc.language | English | |
dc.language.iso | eng | |
dc.publisher | Royal Society of Chemistry | |
dc.publisher.place | United Kingdom | |
dc.publisher.uri | http://www.rsc.org/publishing/journals/DT/Index.asp | |
dc.relation.ispartofstudentpublication | N | |
dc.relation.ispartofpagefrom | 2547 | |
dc.relation.ispartofpageto | 2556 | |
dc.relation.ispartofissue | 15 | |
dc.relation.ispartofjournal | Dalton Transactions: an international journal of inorganic chemistry | |
dc.relation.ispartofvolume | 2005 | |
dc.rights.retention | N | |
dc.subject.fieldofresearch | Inorganic chemistry | |
dc.subject.fieldofresearch | Theoretical and computational chemistry | |
dc.subject.fieldofresearch | Other chemical sciences | |
dc.subject.fieldofresearchcode | 3402 | |
dc.subject.fieldofresearchcode | 3407 | |
dc.subject.fieldofresearchcode | 3499 | |
dc.title | Structural and solid state 31P NMR studies of the four-coordinate copper(I) complexes [Cu(PPh3)3X] and [Cu(PPh3)3(CH3CN)]X | |
dc.type | Journal article | |
dc.type.description | C1 - Articles | |
dc.type.code | C - Journal Articles | |
gro.rights.copyright | © 2005 Royal Society of Chemistry. Please refer to the journal link for access to the definitive, published version. | |
gro.date.issued | 2005 | |
gro.hasfulltext | No Full Text | |
gro.griffith.author | Healy, Peter C. | |