Beiträge zur Komplexchemie der Phosphine und Phosphinoxyde. VII. Schwermetallkomplexe des Diphenylphosphins

Issleib, K.; Wenschuh, Eberhard

doi:10.1002/zaac.19603050103

Cited by 51 publications

(6 citation statements)

References 7 publications

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“…Phosphanido‐bridged complexes of transition metals have a history of almost 50 years: the first member of this series, reported in 1960, is the dimeric palladium(II) complex [Pd(Cl)(μ‐PPh 2 )(PPh 2 H)] 2 ,2 which was at that time not recognised as a phosphanido‐bridged complex 3. In the following years, a lively research led to the synthesis and characterisation of hundreds of new polynuclear compounds characterised by one or more phosphanido groups bridging two (or more) metal atoms.…”

Section: Introductionmentioning

confidence: 99%

Bridging and Terminal (Phosphanido)platinum Complexes

Mastrorilli¹

2008

Eur J Inorg Chem

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The PR2– group (the phosphanido group, according to the modern IUPAC rules) possesses a strong nucleophilicity, a high bridging tendency and a remarkable flexibility. This review addresses the issue of (phosphanido)platinum complexes, subdividing them into terminal and bridging species. Terminal (phosphanido)platinum complexes are usually prepared by deprotonation of a coordinated secondary (or primary) phosphane on a cationic PtII complex, by an appropriate base. The terminally bonded phosphanide group shows no tendency to form multiple bonds with platinum: in all crystallographically characterised Pt complexes, the terminal phosphanido P atom is pyramidal. Due to the high nucleophilicity granted by the presence of the active lone pair on P, terminal (phosphanido)platinum complexes react with molecules such as O2 and S8, and they can be used for the synthesis of dimetallic compounds upon reaction with suitable metal fragments. The known PtI phosphanido‐bridged complexes are dinuclear, diamagnetic and endowed with a strong Pt–Pt bond. The μ‐PPh2 bridge in PtI dimers arises often by (thermal) activation of the P–C bond in coordinated PPh3 or dppm. PtI phosphanido‐bridged complexes are also prepared by reaction of (dichlorido)platinum complexes with reagents such as Na, NaOH, alcohols. For such complexes a multifaceted reactivity, including the substitution of a terminal ligand, the reaction with electrophiles such as H+ and its isolobal analogues, the insertion into the μ‐P–Pt bond, has been reported. Hydridophosphanido complexes are formed by oxidative addition of a P–H bond onto zero‐valent Pt complexes, by protonation of PtI dimers or by action of BH4– on halido species. Dehydrochlorination of secondary (and primary) phosphane complexes gives chlorido complexes which are mostly prepared in the anti‐[(PRR′2)(Cl)Pt(μ‐PR″2)]2 geometry. Chiral complexes are obtained when asymmetric phosphanido P atoms are present in the molecule. A rich coordination chemistry has been developed on organometallic phosphanido Pt complexes bearing the pentafluorophenyl group. In this framework, a great number of Pt complexes of various nuclearity have been crystallographically characterised and their reactivity towards oxidants studied. The class of polynuclear phosphanido Pt complexes is represented by triangulo species, in which the bridging phosphanide group is typically μ‐PPh2 or μ‐PtBu2, by linear complexes of various nuclearity and by bent species stemming from the presence of a triply bridging diphenylphosphanido ligand in the molecule. Applications of phosphanido Pt complexes in catalysis and materials chemistry are also discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Introductionmentioning

confidence: 99%

Bridging and Terminal (Phosphanido)platinum Complexes

Mastrorilli¹

2008

Eur J Inorg Chem

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“…These are reported in Error estimated in value determined from frozen solutions ±0.009. 6 (g) = 1/8(g| | + 2g±). c (g) read directly from solution esr spectra at room temperature.…”

Section: Resultsmentioning

confidence: 99%

“…In this paper we report the results of our esr studies of the low-spin complexes Co[(CH3)2NPF2]8X2, Co-{[(CH8)2N ]2PF} 8X2, and Co(Ph2PH)8Br2. The last complex, whose preparation was reported by Issleib and Wenschul,6 is included in this study because it has been shown by a single-crystal X-ray diffraction study to be a five-coordinate complex, the structure of which lies intermediate between a square pyramid and trigonal bipyramid. 7 We suggest that the unpaired electron orbital of the complexes consists of predominantly 3d,z character plus a small amount of s character.…”

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confidence: 99%

Electron spin resonance and electronic absorption studies of low-spin, five-coordinate complexes of cobalt(II)

Nowlin¹,

Subramanian²,

Cohn³

1972

Inorg. Chem.

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“…it was originally believed to be. 13 In contrast to the numerous3 studies of oxidative addition reactions of zerovalent palladium and platinum complexes, few studies have been conducted with nickel complexes though oxidative additions are implicated in numerous catalytic reactions involving nickel species. 14 The limited number of studies is probably due to the general extreme air sensitivity or lack of reactivity of these species.…”

Section: Methodsmentioning

confidence: 99%