Structural and spectroscopic studies of three-coordinate copper(I) supported by bis(phosphino)borate ligands
- Creators
- Thomas, J. Christopher
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Peters, Jonas C.
Abstract
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 Me2S · 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(Sdouble bond; length as m-dashPMe3) (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.
Additional Information
© 2004 Elsevier Ltd. Received 1 July 2004; accepted 25 August 2004; Available online 28 October 2004. Financial support from the NSF (CHE-0132216) and the DOE (PECASE) is acknowledged. Larry Henling provided assistance with X-ray crystallography. Christine Thomas generously provided a sample of PhB(CH2PtBu2)2. J.C.T. is grateful to the NSF and to the Moore Foundation for graduate research fellowships. Dedicated to Professor Malcolm H. Green, an inspiring organometallic chemist.Additional details
- Eprint ID
- 47585
- Resolver ID
- CaltechAUTHORS:20140730-084937391
- NSF
- CHE-0132216
- Department of Energy (DOE)
- Created
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2014-07-30Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field