Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

There will be scheduled maintenance work beginning on Saturday 15th June 2019 at 8:30 am through to Sunday 16th June 2019 at 11:30 pm (BST).

During this time our website may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 4, 2001
Previous Article Next Article

Metal–metal interactions across bridging elemental carbon chains: a computational study of odd-carbon complexes

Author affiliations

Abstract

Structure, bonding and metal–metal interactions in complexes [LyMCxM′Ly]z+ with odd-carbon chains, and monometallic reference compounds, are investigated at the B3LYP density functional level of theory. The data show strong rhenium–manganese interactions in [(η5-C5H5)(NO)(PH3)ReCxMn(CO)25-C5H5)]+ (x  = 3, 5, 7, 9), as evidenced by bond lengths and orders, charge distributions, and negative homodesmotic energies (which diminish with chain length). Natural bond orbital (NBO) analyses give ground states with highly polarized Re–C bonds, and suggest dominant +Re–(C[double bond, length half m-dash]C)n[double bond, length half m-dash]C[double bond, length half m-dash]Mn as opposed to +Re[double bond, length half m-dash](C[double bond, length half m-dash]C)n[double bond, length half m-dash]C[double bond, length half m-dash]Mn character. The corresponding dirhenium complexes are similar but with dominant Re(–C[triple bond, length half m-dash]C)n–C[triple bond, length half m-dash]Re+ character. The more symmetrical uncharged complexes (η5-C5H5)(CO)2M(1)CxM(2)(CO)25-C5H5) [x  = 3, 5; M(1), M(2) = Re or Mn] exhibit analogous geometric, electronic and homodesmotic energy trends, but have dominant M[double bond, length half m-dash](C[double bond, length half m-dash]C)n[double bond, length half m-dash]C[double bond, length half m-dash]M character. In contrast, (η5-C5H5)(NO)(PH3)ReC3W(OMe)3 which has a ReC[triple bond, length half m-dash]CC[triple bond, length half m-dash]W linkage, shows no significant (net) rhenium–tungsten interactions. All geometric and electronic properties are very close to those of monometallic reference compounds. Homodesmotic energies are near zero, although related triple bond metatheses used preparatively are exothermic. The dimerization of (MeO)3W[triple bond, length half m-dash]CH is exothermic (−14.6 kcal mol−1), giving a methoxy-bridged structure closely resembling literature compounds.

Back to tab navigation

Publication details

The article was received on 31 Oct 2000, accepted on 22 Jan 2001 and first published on 21 Mar 2001


Article type: Paper
DOI: 10.1039/B008786F
New J. Chem., 2001,25, 551-562

  •   Request permissions

    Metal–metal interactions across bridging elemental carbon chains: a computational study of odd-carbon complexes

    H. Jiao and J. A. Gladysz, New J. Chem., 2001, 25, 551
    DOI: 10.1039/B008786F

Search articles by author

Spotlight

Advertisements