Show simple item record

dc.contributor.authorBOWMAKER, GA
dc.contributor.authorENGELHARDT, LM
dc.contributor.authorHEALY, PC
dc.contributor.authorKILDEA, JD
dc.contributor.authorPAPASERGIO, RI
dc.contributor.authorWHITE, AH
dc.date.accessioned2017-05-03T11:09:17Z
dc.date.available2017-05-03T11:09:17Z
dc.date.issued1987
dc.date.modified2008-09-26T08:56:37Z
dc.identifier.issn0020-1669
dc.identifier.doi10.1021/ic00268a023
dc.identifier.urihttp://hdl.handle.net/10072/19582
dc.description.abstractSolid-state 31P NMR spectra, far-infrared spectra, and single-crystal X-ray structure determinations have been recorded for (2-methylpheny1)diphenylphosphine (PPh2-o-tol) and its mononuclear 2: 1 adducts with copper(1) halides, (PPh2-o-tol)2CuX. The solid state ,IP NMR spectrum of the ligand shows a single sharp resonance at -18 ppm with respect to 85% H3P04. The spectra of the 2:l adducts show two sets of overlapping asymmetric quartets for the chloride and bromide and a single broad quartet for the iodide, indicating the presence of at least two crystallographically distinct ligands in the first two compounds and one in the third. Average chemical shift values (ppm) are as follows: C1, -1 1; Br, -11; I, -15. The asymmetry in the line spacing for each quartet is consistent with a trigonal coordination geometry around the copper atom. Far-infrared spectra of each of the metal complexes in the range 50-400 cm-' show strong bands that are assigned to terminal metal-halogen stretching vibrations: Cu-Cl, 290 cm-I; Cu-Br, 220 cm-I; Cu-I, 200 cm-'. The parent ligand crystallizes in the monoclinic space group P2,/c with a = 10.713 (5) A, b = 8.726 (5) A, c = 16.573 (6) A, fi = 90.77 (3)O, and 2 = 4. All three copper structures crystallize in the monoclinic space group C2/c. The CI and Br structures are isomorphous with one complete molecule of (PPh2-o-tol)2CuX comprising the asymmetric unit. For X = CI, a = 22.413 (15) A, b = 16.034 (4) A, c = 19.092 (2) A, @ = 107.04 (4)O, and 2 = 8; for X = Br, a = 22.348 (7) A, b = 16.033 (8) A, c = 19.526 (5) A, fi = 108.73 (2)O, and 2 = 8. However, for X = I, a = 18.665 (5) A, b = 10.006 (2) A, c = 19.764 (5) A, fi = 115.29 (2)O, and Z = 4, with the two ligands related by symmetry and the Cu-I bond sited on the 2-fold rotation axis. For X = CI, Cu-P, Cu-P, Cu-X, and P-Cu-P = 2.241 (2) A, 2.257 (2) A, 2.205 (2) A, and 126.96 (7)O respectively; for X = Br, the values are 2.240 (2) A, 2.255 (2) A, 2.336 (1) A, and 127.89 (7)O, respectively; and for X = I, Cu-P, Cu-I, and PCu-P = 2.255 (1) A, 2.507 (1) A, and 126.36 (7)O, respectively. Both Cu-P and Cu-X distances are similar to the corresponding values for (PPh3)2CuX compounds. However, as a consequence of changes in steric profile, the conformational structure of each ligand about the Cu-P bonds with respect to Cu-X is significantly different.
dc.description.peerreviewedYes
dc.description.publicationstatusYes
dc.languageEnglish
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.publisher.placeWashington, United States
dc.publisher.urihttp://pubs.acs.org/journals/inocaj/index.html
dc.relation.ispartofstudentpublicationN
dc.relation.ispartofpagefrom3533
dc.relation.ispartofpageto3538
dc.relation.ispartofjournalInorganic Chemistry
dc.relation.ispartofvolume26
dc.rights.retentionY
dc.subject.fieldofresearchInorganic chemistry
dc.subject.fieldofresearchPhysical chemistry
dc.subject.fieldofresearchOther chemical sciences
dc.subject.fieldofresearchcode3402
dc.subject.fieldofresearchcode3406
dc.subject.fieldofresearchcode3499
dc.titleLewis-base adducts of group 11 metal(I) compounds. 32. Steric effects in the 2:1 adducts of (2-methylphenyl)diphenylphosphine with copper(I) halides
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
gro.rights.copyright© 1987 American Chemical Society. Self-archiving of the author-manuscript version is not yet supported by this publisher. The contents of this journal can be freely accessed online via the ACS web page. Use hypertext link above to access the ACS website.
gro.date.issued1987
gro.hasfulltextNo Full Text
gro.griffith.authorHealy, Peter C.


Files in this item

FilesSizeFormatView

There are no files associated with this item.

This item appears in the following Collection(s)

  • Journal articles
    Contains articles published by Griffith authors in scholarly journals.

Show simple item record