Syntheses and NMR spectroscopic characterizations of the bimetallic complexes: (CO)5Mo(η-R2PXPR′2) Mo(CO)5 (R2,R′2 = Ph2, OCH2CMe2CH2O; X = O, NHCH2CH2NH); the structure of...

Academic Article

Abstract

  • Title full: Syntheses and NMR spectroscopic characterizations of the bimetallic complexes: (CO) Mo(η-R PXPR′ ) Mo(CO) (R ,R′ = Ph , OCH CMe CH O; X = O, NHCH CH NH); the structure of (CO) Mo- (η-Ph POP(OCH CMe CH O)) Mo(CO) . Bimetallic complexes of the types (CO) Mo(η-R PXPR′ )Mo(CO) (R , R′ = Ph , OCH CMe CH O; X = O, NHCH CH NH) have been synthesized by the reactions of Mo(CO) (R′ PX) (X = Cl, Br) with either [Et NH][Mo(CO) (R PO)] or Mo(CO) (R PNHCH CH NH ). These reactions provide a precise control over the coordination environment of the metals because the bridging, bidentate ligand is formed after the P-donor groups have been coordinated to the metal centers. The C and P NMR spectra of the complexes are discussed. The C NMR spectra of the complexes containing the R POPR′ ligands varies significantly with the nature of the R and R′ groups. The resonances that are coupled to P are apparent quintets (A portion of an AXX′ spin system) for. the symmetrical complexes and doublets (A portion of an AXY spin system with no A-Y coupling) for the unsymmetrical complexes. The X-ray crystal structure of (CO) Mo(η-Ph POP(OCH CM CH O))Mo(CO) has been determined. The complex crystallizes in the monoclinic space group P2 /c (a 8.792(2), b 33.946(5), c 10.762(1) Å; β 104.02(1)°; V 3116.3(6) Å ; Z = 4). The structural data suggest that the Ph P group is a better electron donor (poorer electron acceptor) than is the P(OCH CMe CH O) group and are consistent with NMR spectroscopic results. The P(OCH CMe CH O) ring is in a chair conformation, which is slightly flattened at the P, with Mo(CO) group in the equatorial position. © 1988. 5 2 2 5 2 2 2 2 2 2 2 2 5 2 2 2 2 5 5 2 2 5 2 2 2 2 2 2 2 2 5 2 3 5 2 5 2 2 2 2 2 2 2 2 5 2 2 2 2 5 1 2 2 2 2 2 2 2 5 13 31 13 3
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    Digital Object Identifier (doi)

    Author List

  • Gray GM; Watt W
  • Start Page

  • 149
  • End Page

  • 161
  • Volume

  • 349
  • Issue

  • 1-2