Synthesis of diphenylphosphine palladium complexes

Giannandrea, Roberto; Mastrorilli, Piero; Nobile, Cosimo Francesco

doi:10.1016/s0020-1693(98)00269-2

Cited by 24 publications

(9 citation statements)

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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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“…Thus, the chemistry of phosphido-bridged derivatives of the main group elements [1][2][3] or transition metals [4][5][6] has been a matter of interest for various research groups in the last few years. While there are many phosphido complexes with metals, mainly of groups 6 7-12 or 10, [13][14][15][16][17][18][19][20] the chemistry of gold derivatives has experienced less progress in this field of research in spite of the possible catalytic behaviour of di-and polynuclear phosphido-bridged compounds. 21 This is an interesting field of research, because the substitution of one or more protons by metal atoms allows the synthesis of homo-or heteropolynuclear compounds in which the presence of a small bridging atom, such as phosphorus, may give rise to intermetallic contacts, which, as is known, are often responsible for surprising and interesting optical properties, such as luminescence, area with an increasing importance in the last years.…”

Section: Introductionmentioning

confidence: 99%

Gold Phosphide Complexes

Fernández

Taguna

Olmos

2007

J. Chil. Chem. Soc.

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“…Unfortunately, only the X-ray crystallographic data for this compound are available. The 31 P{ 1 H} NMR spectra of known di-m-PPh 2 Pd(II) complexes usually have the signals of the bridging PPh 2 group between À100 and À140 ppm [19,20,34,35,37]. We were able to isolate two complexes, 4a,c, which presumably have dimeric cyclopalladated structure with two bridging PPh 2 ligands.…”

Section: Structure Confirmationmentioning

confidence: 88%

“…Di-m-PPh 2 complexes of Pd(II) and especially Pt(II) are well known [19,20,34,35]. However, to the best of our knowledge, only one cyclometallated derivative of this type has been reported, the Pt(II) complex derived from 7,8-benzoquinoline [36].…”

Section: Structure Confirmationmentioning

confidence: 99%

Reactivity of dimeric cyclopalladated complexes with an (sp)C–Pd bond toward KPPh2

Dickmu

Korte

Smoliakova

2015

Journal of Organometallic Chemistry

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a b s t r a c tReactions of KPPh 2 with dimeric C,N, C,P and C,S cyclopalladated complexes (CPCs) 1aÀg containing an (sp 3 )CePd bond were investigated. The CPCs used in the study were obtained from D-camphor O-The dichloro-bridged CPCs 1a,b,d,f,g and the diacetato-bridged analog m-OAc-1d reacted with 4.5 equiv.of KPPh 2 at room temperature in THF to give either phosphines 2a,b or phosphine oxides 8d,f,g in 20 e51% yield. Complexes 1a,b,d reacted with 1 equiv. of KPPh 2 to produce the corresponding m-chloro-mdiphenylphosphido-CPCs 3a,b,d in 33e56% yield. In the reaction of CPC 1c with 4.5 equiv. of KPPh 2 , complex 4c with two PPh 2 bridging ligands was isolated in 36% yield. Structures of phosphines 2a,b, phosphine oxides 8a,d,f,g as well as complexes 3a,b,d and 4c were confirmed by 1 H, 13 C{ 1 H} and 31 P{ 1 H} NMR spectroscopy.

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Synthesis of diphenylphosphine palladium complexes

Cited by 24 publications

References 4 publications

Bridging and Terminal (Phosphanido)platinum Complexes

Bridging and Terminal (Phosphanido)platinum Complexes

Gold Phosphide Complexes

Reactivity of dimeric cyclopalladated complexes with an (sp)C–Pd bond toward KPPh2

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