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Structural and spectroscopic studies of three-coordinate copper(I) supported by bis(phosphino)borate ligands

Polyhedron, ISSN: 0277-5387, Vol: 23, Issue: 17, Page: 2901-2913
2004
  • 37
    Citations
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  • 10
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Metric Options:   Counts1 Year3 Year

Metrics Details

  • Citations
    37
    • Citation Indexes
      37
  • Captures
    10

Article Description

The bis(phosphino)borates [( p - t BuPh) 2 B(CH 2 PPh 2 ) 2 ][ASN] ( 1 [ASN]; ASN = 5-azonia-spiro[4.4]nonane), [Ph 2 B(CH 2 P i Pr 2 ) 2 ]Li(THF) 2 ( 2 [Li]), and [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ] − ( 3 [Li] and 3 [Tl]) react with copper(I) reagents to generate anionic and neutral complexes. Reaction of 1 [ASN] with CuI provides the 1:1 adduct [[( p - t BuPh) 2 B(CH 2 PPh 2 ) 2 ]CuI][ASN] ( 4 ). CuCl reacts with 3 [Li] in THF to afford [[(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]CuCl][Li(THF) 4 ] ( 5 ), along with a minor byproduct, the three-coordinate bis(phosphine) adduct {(3,5-Me 2 Ph)B(CH 2 P t Bu 2 ) 2 }CuCl ( 6 ). An analogous neutral complex, {PhB(CH 2 P t Bu 2 ) 2 }CuCl ( 7 ), can be synthesized directly by reacting CuCl with the neutral phosphino borane PhB(CH 2 P t Bu 2 ) 2. Reaction of the substituted copper(I) halide Me 2 S · CuBr with 3 [Tl] provides the anionic dimer complex [{[(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]Cu} 2 (μ-Br)]Tl ( 8 ). The neutral solvent adducts [Ph 2 B(CH 2 P i Pr 2 ) 2 ]Cu(NCCH 3 ) ( 9 ) and [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]Cu(NCCH 3 ) ( 10 ) are prepared by the reactions between [Cu(CH 3 CN) 4 ][PF 6 ] and 2 [Li] or 3 [Li], respectively. Neutral 10 is a useful precursor to several other neutral species via substitution of the labile acetonitrile ligand, including [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]Cu(PMe 2 Ph)( 11 ), [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]Cu(S PMe 3 ) ( 12 ), [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ] Cu(2,6-lutidine) ( 13 ), and [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]Cu(CN t Bu) ( 14 ). Attempts to isolate a neutral monocarbonyl adduct, [(3,5-Me 2 Ph) 2 B(CH 2 P t Bu 2 ) 2 ]Cu(CO) ( 15 ), are frustrated by the high lability of the CO ligand. The solid-state crystal structures of complexes 6, 8, 9, 10, and 11 have been determined and are described.

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