Heterodifunctional ligands derived from monooxidized Bis(phosphino)amines. Synthesis and transition metal (Molybdenum(0), Tungsten(0), Rhodium(I), Palladium(II), and Platinum(II)) complexes of (Diphenylphosphino)(diphenylphosphinothioyl)- and (Diphenylphosphino) (diphenylphosphinoselenoyl)phenylamine, Ph[sub 2]PN(Ph)P(E)PH[sub 2] (E = S, Se). Crystal and molecular structure of the Pt(II) Complex [Cl[sub 2]P[ovr tPPh[sub 2]N(Ph)P(S)]Ph[sub 2]][center dot]H[sub 2]O

Bis(diphenylphosphino)phenylamine can be selectivity oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoyl products Ph[sub 2]PN(PH)PPh[sub 2]=E, (E = S, Se). These compounds act as bidentate chelate ligands toward metal complexes forming (CO)[sub 4]M(LL) (M = Mo, W...

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Published inInorganic chemistry Vol. 32:25
Main Authors Balakrishna, M.S., Klein, R., Uhlenbrock, S., Pinkerton, A.A., Cavell, R.G.
Format Journal Article
LanguageEnglish
Published United States 08.12.1993
Subjects
400201 - Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
AMINES
CHEMICAL PREPARATION
COMPLEXES
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PALLADIUM COMPLEXES
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PLATINUM COMPLEXES
RESONANCE
RHODIUM COMPLEXES
SELENIUM COMPOUNDS
SPECTROSCOPY
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
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Summary:Bis(diphenylphosphino)phenylamine can be selectivity oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoyl products Ph[sub 2]PN(PH)PPh[sub 2]=E, (E = S, Se). These compounds act as bidentate chelate ligands toward metal complexes forming (CO)[sub 4]M(LL) (M = Mo, W), CO(Cl)Rh(LL), and Cl[sub 2]M(LL), (M = Pt, Pd) where (LL) is the thioyl or selenoyl derivative of the aminobis(phosphine). IR and NMR data are given for all complexes. The carbonyl infrared stretching frequencies show that the chelates form with the phosphine cis to any CO which is present. The [sup 31]P NMR of all complexes of two doublets except for the Rh complexes wherein the Rh spin also couples to phosphorous to produce two doublets of doublets. The [sup 2]J[sub PP] values range from 56 to 112 Hz. [sup 1]J[sub PSe] coupling provide valuable assistance for the assignment of the phosphorus resonances which range widely from 55 to 126 ppm for P[sup III] and from 60 to 80 ppm for the P[sup v] case. Assignment of P[sup III] and P[sup V] signals, which invert relative shift positions on occasion, is aided by the analysis of appropriate spin satellites arising from the substituents. It is concluded that coordination shifts for P[sup III] are always positive, ranging from 22 ppm for Pt[sup II] complexes to 70 ppm for Rh[sup I] complexes. Coordination shifts for P[sup V] centers are much smaller, e.g. 0.12 ppm, and in some cases the coordination shifts for the P[sup V] centers are negative versus the free ligand.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00077a005