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Bis(phosphino)borates:  A New Family of Monoanionic Chelating Phosphine Ligands

Thomas, J. Christopher and Peters, Jonas C. (2003) Bis(phosphino)borates:  A New Family of Monoanionic Chelating Phosphine Ligands. Inorganic Chemistry, 42 (17). pp. 5055-5073. ISSN 0020-1669. doi:10.1021/ic034150x.

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The reaction of dimethyldiaryltin reagents Me_(2)SnR_(2) (R ) Ph (1), p-MePh (2), m,m-Me_(2)Ph (3), p-tBuPh (4), p-MeOPh (5), p-CF_(3)Ph (6)) with BCl_(3) provided a high-yielding, simple preparative route to the corresponding diarylchloroboranes R_(2)BCl (R ) Ph (10), p-MePh (11), m,m-Me2Ph (12), p-tBuPh (13), p-MeOPh (14), p-CF_(3)Ph (15)). In some cases, the desired diarylchloroborane was not formed from an appropriate tin reagent Me_(2)SnR_(2) (R ) o-MeOPh (7), o,o-(MeO)_(2)Ph (8), o-CF_(3)Ph (9)). The reaction of lithiated methyldiaryl- or methyldialkylphosphines with diarylchloroboranes or dialkylchloroboranes is discussed. Specifically, several new monoanionic bis(phosphino)borates are detailed: [Ph_(2)B(CH_(2)PPh_(2))_(2)] (25); [(p-MePh)_(2)B(CH_(2)PPh_(2))_(2)] (26); [(p-^(t)BuPh)_(2)B(CH_(2)PPh_(2))_(2)] (27); [(p-MeOPh)_(2)B- (CH_(2)PPh_(2))_(2)] (28); [(p-CF_(3)Ph)_(2)B(CH_(2)PPh_(2))_(2)] (29); [Cy_(2)B(CH_(2)PPh_(2))_(2)] (30); [Ph_(2)B(CH_(2)P{p-^(t)BuPh}_(2))_(2)] (31); [(p-MeOPh)_(2)B- (CH_(2)P{p-^(t)BuPh}_(2))_(2)] (32); [Ph_(2)B(CH_(2)P{p-CF_(3)Ph}_(2))_(2)] (33); [Ph_(2)B(CH_(2)P(BH_(3))(Me)_(2))_(2)] (34); [Ph_(2)B(CH_(2)P(S)(Me)_(2))_(2)] (35); [Ph_(2)B(CH_(2)PiPr_(2))_(2)] (36); [Ph_(2)B(CH_(2)P^(t)Bu_(2))_(2)] (37); [(m,m-Me_(2)Ph)_(2)B(CH_(2)P^(t)Bu_(2))_(2)] (38). The chelation of diarylphosphine derivatives 25-33 and 36 to platinum was examined by generation of a series of platinum dimethyl complexes. The electronic effects of substituted bis(phosphino)borates on the carbonyl stretching frequency of neutral platinum alkyl carbonyl complexes were studied by infrared spectroscopy. Substituents remote from the metal center (i.e. on boron) have minimal effect on the electronic nature of the metal center, whereas substitution close to the metal center (on phosphorus) has a greater effect on the electronic nature of the metal center.

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Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2003 American Chemical Society. Received February 12, 2003. The authors acknowledge Dr. Biaxin Qian and Connie Lu for synthetic assistance. Larry Henling, Dr. Michael Day, and Theodore Betley are acknowledged for their assistance with X-ray crystallography. J.C.T. is grateful to the NSF and to the Moore Foundation for graduate research fellowships. The authors acknowledge financial support from the NSF (Grant CHE-0132216), the ACS Petroleum Research Fund, and the Dreyfus Foundation.
Funding AgencyGrant Number
NSF Graduate Research FellowshipUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
ACS Petroleum Research FundUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Issue or Number:17
Record Number:CaltechAUTHORS:20140722-105001149
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Official Citation:Bis(phosphino)borates:  A New Family of Monoanionic Chelating Phosphine Ligands J. Christopher Thomas and and Jonas C. Peters Inorganic Chemistry 2003 42 (17), 5055-5073
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47396
Deposited On:22 Jul 2014 21:08
Last Modified:10 Nov 2021 17:39

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