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Synlett 1991; 1991(10): 671-676
DOI: 10.1055/s-1991-21984
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Phosphorus-Bridging Carbonyl Derivatives: Organophosphorus Analogues of Aldehydes and Ketones

R. B. King*
  • *Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA
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Publication Date:
13 March 2002 (online)

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1. Introduction 2. Synthesis of Phosphorus-Bridging Carbonyl Derivatives 3. Chemical Reactivity of Phosphorus-Bridging Carbonyl Derivatives 3.1. Reduction Reactions 3.2. Acylation Reactions 3.3. Extrusion of the Phosphorus-Bridging Carbonyl Group 4. Conclusion

Reactions of sodium tetracarbonylferrate(-II), Na2Fe(CO)4, with sterically hindered aminodichlorophosphines, R2NPCl2 (R2N = diisopropylamino, dicyclohexylamino, and 2,2,6,6-tetramethylpiperidino), in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R2NP)2COFe2(CO)6 as the major products. The phosphorus-bridging carbonyl group in (iPr2NP)2COFe2(CO)6 has been found to undergo the following types of reactions: (1) Reduction such as reactions with sodium borohydride or alkyllithiums, RLi (R = Me, Bu), to give (iPr2NP)2C(R)OHFe2(CO)6, with lithium aluminum hydride to give [iPr2NPHCHPN(iPr)2]Fe2(CO)6, or with sodium amalgam to give the anion [iPr2NPCOPFe2(CO)6]-, which can be trapped by reactions with chlorotrimethyltin, di-tert-butylchlorophosphine, or dichloro(diisopropylamino)phosphine; (2) Acylation such as reactions with phosphonium methylides R3P=CH2 (R = Me, Me2N, Ph, p-MeC6H4), to give [(iPr2NPH)(iPr2NPCOCHPR3)]Fe2(CO)6; (3) Extrusion such as reactions with alcohols, ROH (R = Me, Et), to give (iPr2NPOR) (iPr2NPH)Fe2(CO)6 or with aldehydes and ketones, R1R2C=O (R1 = R2 = H, Ph; R1 = Ph, R2 = H, Me; R1 + R2 = -(CH2)5-) to give [(iPr2NP)2OCR1R2] Fe2(CO)6.

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