Phosphorus-31-phosphorus-31 coupling in metal complexes containing two different phosphorus ligands

Ogilvie, F. B.; Keiter, Richard L.; Wulfsberg, Gary; Verkade, J. G.

doi:10.1021/ic50081a024

Cited by 19 publications

(4 citation statements)

References 2 publications

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“…The reaction of Mo(CO) 4 (NBD) with 2 equiv of 8b in CHCl 3 furnished a cis−trans mixture of 8l in 32% yield. The IR spectrum of 8l showed six well-separated CO bands (2029, 2022, 1924, 1907, 1889, 1878 cm -1 ) which contrasts the three or four CO bands reported for cis -Mo(CO) 4 [P(NMe 2 ) 3 ] 2 , ,, the three CO bands (and sometimes one band) reported for trans -Mo(CO) 4 [P(NMe 2 ) 3 ] 2 ,19c and the three (or sometimes two) CO bands reported for trans -Mo(CO) 4 [P(NMeCH 2 ) 3 CMe] 2 19c. The observation of six CO bands for 8l is consistent with a mixture of cis and trans isomers.…”

Section: Resultsmentioning

confidence: 77%

Comparisons of Phosphorus Ligation Properties in P(CH₂NR)₃P

et al. 2007

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Bicyclic P(CH2NMe)3P was synthesized, and its reactions with MnO2, elemental sulfur, p-toluenesulfonyl azide, BH3.THF, and W(CO)5(THF) were shown to furnish a variety of products in which the PC3 and/or the PN3 phosphorus are oxidized/coordinated. In contrast, reactions of the previously known P(CH2NPh)3P with Mo(0) and Ru(II) precursors were shown to afford products in which only the PC3 phosphorus is coordinated. The contrast in reactivity of P(CH2NR)3P (R = Me, Ph) with the aforementioned reagents is discussed in terms of steric and electronic factors. The new compounds are characterized by analytical and spectroscopic (IR, 1H, 31P, and 13C NMR) methods. The results of crystal and molecular structure X-ray analyses of the previously known compounds P(CH2O)3P and P(CH2NPh)3P and 6 of the 14 new compounds obtained in this investigation are presented. Salient features of these structures and the analysis of the Tolman cone angles calculated from their structural parameters are discussed in terms of the effects of constraint in the bicyclic moieties. Evidence is presented for greater M-P sigma bonding effects on coordination of the PC3 phosphorus of P(CH2NR)3P (R = Me, Ph) than are present in PMe3 analogues of group 6B metal carbonyls. From 1JBP data on the BH3 adducts of P(CH2NMe)3P, it is suggested that the free bases MeC(CH2NMe)3P < P(CH2NMe)3P < (Me2N)3P < P(MeNCH2CH2)3N increase in Lewis basicity at the PN3 phosphorus in the order shown. Substantial differences in 31P chemical shifts in the bicyclic compounds discussed herein relative to their acyclic analogues do not seem to be associated with the relatively small bond angle changes that occur around either the PN3 or the PC3 trivalent phosphorus atoms.

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Section: Resultsmentioning

confidence: 77%

Comparisons of Phosphorus Ligation Properties in P(CH₂NR)₃P

et al. 2007

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“…Furthermore, if the two trans tertiary phosphines were nonequivalent, the NMR spectra would show two doublets, perturbed doublets, or perturbed triplets. 19 these reasons is decisive, these are all in favor of perpendicular geometry of the aroyl group. The spectrum of 2b in dichloromethane or in benzene showed also two triplets, but with very little separation.…”

Section: Resultsmentioning

confidence: 99%

Isolation and methylation of aroylnickel intermediates derived by carbonylation of trans-aryl(pentachlorophenyl)bis(phenyldimethylphosphine)nickel(II) compounds

Wada¹,

Asada²,

Oguro³

1978

Inorg. Chem.

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“…Found: C, 61.94; , 4.81; P, 7.73; = 74. (19) Preparation of [Rh(l,3-butadiene)¡ P(C6II3)3 j2]~PFs~. A preparation identical with (18) was carried out, employing 500 mg of [Rh(NBD){P(C6H5)3 ¡2]+PF6" and 1,3-butadiene; it gave 430 mg (90%) of product:…”

Section: Methodsmentioning

confidence: 99%

Preparation and properties of some cationic complexes of rhodium(I) and rhodium(III)

Osborn¹,

Schrock²

1971

J. Am. Chem. Soc.

384

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Cationic complexes of the type [Rh(diene)L2]+ (diene = 1,5-cyclooctadiene (COD) or norbornadiene (NBD), L = tertiary phosphine or arsine ligand) have been prepared by several routes. These complexes serve as useful intermediates for the synthesis of many other cationic rhodium(I) and rhodium(III) species. Treatment of [Rh(COD){P(CgH5)s}2]+ with basic phosphines, L, leads to the isolation of the cations [RhL4]-. Under identical

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Phosphorus-31-phosphorus-31 coupling in metal complexes containing two different phosphorus ligands

Cited by 19 publications

References 2 publications

Comparisons of Phosphorus Ligation Properties in P(CH₂NR)₃P

Comparisons of Phosphorus Ligation Properties in P(CH₂NR)₃P

Isolation and methylation of aroylnickel intermediates derived by carbonylation of trans-aryl(pentachlorophenyl)bis(phenyldimethylphosphine)nickel(II) compounds

Preparation and properties of some cationic complexes of rhodium(I) and rhodium(III)

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Phosphorus-31-phosphorus-31 coupling in metal complexes containing two different phosphorus ligands

Cited by 19 publications

References 2 publications

Comparisons of Phosphorus Ligation Properties in P(CH2NR)3P

Comparisons of Phosphorus Ligation Properties in P(CH2NR)3P

Isolation and methylation of aroylnickel intermediates derived by carbonylation of trans-aryl(pentachlorophenyl)bis(phenyldimethylphosphine)nickel(II) compounds

Preparation and properties of some cationic complexes of rhodium(I) and rhodium(III)

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Comparisons of Phosphorus Ligation Properties in P(CH₂NR)₃P

Comparisons of Phosphorus Ligation Properties in P(CH₂NR)₃P