Cumulated double bond systems as ligands

Meij, Ruud; Stufkens, Derk J.; Vrieze, K.; Brouwers, A. M. F.; Overbeek, A. R.

doi:10.1016/s0022-328x(00)90428-5

Cited by 22 publications

(6 citation statements)

References 22 publications

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“…Thus the <5Pa value where the phosphorus atoms are in a 5-membered ring is +78, whereas the <5Pb value where the phosphorus is in two 5-membered rings is +110.2, or 30 ppm further deshielded. Reaction of W(CO)4(Ph2PCH=CH2)2 with Ph2PH under free-radical conditions gives 30.31 The resonance Ph2 30 at -20 ppm is assigned to Pc since this is close to the free ligand value of PPh2Pr (-17.6) and the resonances at +4.0 ppm is assigned to Pb because of its resemblance to the 6P value for W(CO)4(dppp).17 The series M(CO)3BrL (Table III) reveals a <5P(dppm) -5P(dppe) of 77 for Mn and 68 for Re. 32 Although no analogues are available for calculation of AR values, these data reveal the relative shielding and deshielding caused by the 4-and 5-membered rings.…”

Section: Previous Methods Of Determining Chelation In Phosphine Compl...mentioning

confidence: 90%

.DELTA.R-ring contributions to phosphorus-31 NMR parameters of transition-metal-phosphorus chelate complexes

Garrou¹

1981

Chem. Rev.

1,005

505

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Section: Previous Methods Of Determining Chelation In Phosphine Compl...mentioning

confidence: 90%

.DELTA.R-ring contributions to phosphorus-31 NMR parameters of transition-metal-phosphorus chelate complexes

Garrou¹

1981

Chem. Rev.

1,005

505

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“…The methylplatinum dimer [(Me)(PMe 2 Ph)Pt(μ‐PPh 2 )] 2 ( 106 ) is formed by reaction of cis ‐[Pt(Me) 2 (PMe 2 Ph) 2 ] with PHPh 2 84. The phenylplatinum complex [Pt 2 S{N(6‐μ‐ N ‐4,5‐Me 2 C 6 H 2 )}(μ‐PPh 2 )(PPh 3 ) 2 Ph] ( 107 ) is obtained from reaction of [Pt(C 2 H 4 )(PPh 3 ) 2 ] with 5,6‐dimethyl‐2,1,3‐benzothiadiazole (Scheme ) 85. The 7,8‐benzoquinolinate complex [Pt(bzq)(μ‐PPh 2 )] 2 ( 108 ) forms when [Pt(bzq)(μ‐Cl)] 2 reacts with PHPh 2 and Et 3 N (Scheme ) 86…”

Section: Phosphanido‐bridged Dinuclear Platinum Complexesmentioning

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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“…"Sterically induced bending" (Figure 1c), which appears a more rational strategy to the synthesis of closely bridged bimetallic complexes, was recently documented. 9 For example, roof-shaped alkyldithiolato-10 or alkyldiphosphidobridged 11 binuclear complexes have been prepared and characterized. In these cases, the presence of the alkyl linker enforces them sterically to adopt the desired conformation.…”

Section: Introductionmentioning

confidence: 99%

Roof-Shaped Halide-Bridged Bimetallic Complexes via Ring Expansion Reaction

2006

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Binucleating behavior of rigid triptycene-based ligands has been studied. It has been demonstrated that trans-spanned transition-metal mononuclear complexes bearing 1,8-bis(diisopropylphosphino)triptycene (L1) and 1-diisopropylphosphino-8-diphenylphosphinotriptycene (L2) react with an appropriate transition-metal precursor via a ring-expansion pathway to form unusual bimetallic quasi-closed structures. New palladium and rhodium complexes featuring strongly bent (ca. 115 degrees ) M2(mu-Cl2) cores with very closely spanned metal centers (less than 3 A) have been prepared using the described ring-expansion reaction and have been fully characterized. Despite a constrained arrangement of the binuclear system, halogen bridges in all new compounds were stable in both the solid state and solution showing no tendency for dissociation even in the presence of added Lewis bases. Spontaneous resolution of the dissymmetric Pd2(mu-Cl)2Cl2(1-diisopropylphosphino-8-diphenylphosphinotriptycene) (2) into enantiopure antipodes is discussed as well.

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Cumulated double bond systems as ligands

Cited by 22 publications

References 22 publications

.DELTA.R-ring contributions to phosphorus-31 NMR parameters of transition-metal-phosphorus chelate complexes

.DELTA.R-ring contributions to phosphorus-31 NMR parameters of transition-metal-phosphorus chelate complexes

Bridging and Terminal (Phosphanido)platinum Complexes

Roof-Shaped Halide-Bridged Bimetallic Complexes via Ring Expansion Reaction

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