C–H and P–C(Ph) activation competitive processes caused by interaction with the solvate [cis-Pt(C6F5)2(thf)2]

Berenguer, Jesús R.; Bernechea, María; Lalinde, Elena

doi:10.1039/b705041k

Cited by 7 publications

(5 citation statements)

References 92 publications

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“…As is shown in Figure 4b, each water molecule is simultaneously hydrogen bonded to two phosphinite ligands of two neighboring diplatinum complexes, giving rise to a dimer generated at equivalent positions (−x, −y, −z). A similar feature has been observed in the mononuclear phosphinito complex [22,[28][29][30][31] for which the existence of a through-ring Pt-Pt bonding interaction has been suggested on the basis of theoretical calculations [32]. The Pt-C(1) (2.036(4) Å) and Pt-P distances (2.2409(10)-2.3255(10) Å) and structural details of the terminal C≡CSiMe3 (C≡C 1.192(6) Å; Pt(1)-C(1)-C(2) 177.1(4)º; C(1)-C(2)-Si(1) 177.2(4)º) are unexceptional for these ligands.…”

Section: X-ray Structure Ofsupporting

confidence: 78%

“…The 195 Pt resonances (δ −5,582 and δ −5,562) were attributed to Pt 1 and Pt 2 , respectively, by combined analysis of the 195 Pt{ 1 H} NMR, 31 The 13 C{ 1 H} NMR spectrum in n-hexane showed, beside the cyclohexyl signals, a sharp singlet at δ 1.5 attributable to SiMe3 and two low-field signals flanked by 195 Pt satellites at δ 129.9 (doublet of doublets) and at δ 116.6 (doublet) attributable to the quaternary carbons C 1 and C 2 (Scheme 2). The chemical shift and the multiplicity of these signals confirm the σ-coordination of the (trimethylsilyl)acetylide to Pt.…”

Section: Synthesis and Spectroscopic Features Of The Hydride/acetylidmentioning

confidence: 99%

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A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene

et al. 2014

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The reaction of (trimethylsilyl)acetylene with the phosphinito phosphanido Pt(I) complex [(PHCy2)Pt(μ-PCy2){κ 2 P,O-μ-P(O)Cy2}Pt(PHCy2)](Pt-Pt) (1) results in the protonation of the Pt-Pt bond with the formation of the bridging hydride complex [(PHCy2)(Me3SiC≡C)Pt(μ-PCy2)(μ-H) Pt(PHCy2){κP-P(O)Cy2}](Pt-Pt) (2), which was characterized by spectroscopic, spectrometric and XRD analyses. Complex 2 exhibits in the solid state at 77 K a long-lived, weak, orange emission assigned as metal-metal to ligand charge transfer (MMLCT) (L = alkynyl) due to the presence of a very short Pt···Pt distance [2.8209(2) Å]. Reaction of 2 with etherate HBF4 results in the selective protonation of the phosphinito ligand to afford the species [(PHCy2)(Me3SiC≡C)Pt(μ-PCy2)(μ-H) Pt(PHCy2){κP-P(OH)Cy2}](Pt-Pt)[BF4] ([3]BF4).

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Section: X-ray Structure Ofsupporting

confidence: 78%

Section: Synthesis and Spectroscopic Features Of The Hydride/acetylidmentioning

confidence: 99%

A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene

et al. 2014

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“…Reaction of 95 with PPh 3 in acetone yields [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(PPh 3 )(Cl)] – ( 100 ), while reaction of 95 with [Ag(PPh 3 )ClO 4 ] gives the unsaturated species [(C 6 F 5 ) 2 Pt(μ‐PPh 2 ) 2 Pt(PPh 3 )] (Pt–Pt) ( 101 ) containing a dative Pt→Pt bond 78. The structurally related complex [(C 6 F 5 ) 2 Pt(μ‐PPh 2 )(μ‐Ph)Pt(PPh 3 )] (Pt–Pt) ( 102 ) is one of the products obtained from reactions of cis ‐[Pt(C 6 F 5 ) 2 (thf) 2 ] with [Pt(η 2 ‐alk)(PPh 3 ) 2 ] (alk = H 2 C=CH 2 , HC≡CSiMe 3 or HC≡C t Bu) 79…”

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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“…It is worth noting that although numerous examples of double (μ-CtCR) 2 34,44,45,[71][72][73][74][75][76][77][78][79][80] and mixed (μ-CtCR)(μ-X) (X = hydride, [81][82][83][84] PPh 2 CtCR 72,78 ) diplatinum complexes have been reported, as far as we know, complexes 1-3 are the first representative examples in platinum chemistry of homobimetallic complexes stabilized by a rare heterobridged mixed (μ-X)-(μ-CtCR) system. As is shown in Figure 1, due to the σ/π coordination of the acetylide ligand, the coordination environment of both Pt atoms is different.…”

Section: ' Results and Discussionmentioning

confidence: 99%

Remarkable Influence of the Cyclometalating Ligand on the Nuclearity and Properties of Heterobridged (μ-X)(μ-C≡CR) Platinum(II) Complexes

et al. 2011

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Partial dehalogenation reaction of [Pt(C ∧ N)(μ-Cl)] 2 [C ∧ N = 2,6-diphenylpyridinate (dppyH), 7,8-benzoquinolate (bzq)] with NaCtC t Bu (or HCtC t Bu/NEt 3 /CuI) proceeds with formation of binuclear ([{Pt(dppyH)} 2 (μ-Cl)(μ-CtC t Bu)], 1) or tetranuclear ([Pt 2 (bzq) 2 (μ-Cl)(μ-CtC t Bu)] 2 , 4) complexes, depending on the nature of the cyclometalated ligand. Similar halide-bridged complexes 2, 3, 5, and 6 have also been prepared. The X-ray structures of 1, 4, and 5 reveal the selective formation in all cases of the isomer having the bridging chlorine atom located in a trans position to the metalated carbon atoms of two Pt(C ∧ N) units. In 4 and 5, the tetrahedral Pt 4 core is additionally stabilized by short Pt 3 3 3 Pt and π 3 3 3 π intramolecular bonding interactions, which have influence on their photophysical properties. The lower lying absorption bands are ascribed to mixed 1 MLCT [PtfdppyH]/ 1 LL 0 CT [CtCR/XfdppyH] (complexes 1-3) or to 1 MMLL 0 CT transitions (L = CtCR, L 0 = bzq) (complexes 4-6, TD-DFT). Complexes 1-3 are nonemissive. By contrast, the tetranuclear clusters are brightly emissive at 77 K (solid state, frozen CH 2 Cl 2 ), exhibiting an unstructured orange emission (560-580 nm). This emission has been attributed, according to computational studies of the frontier orbitals in the optimized T 1 state of 5, to an excited state of large [Pt(d)/π(CtCR)/Pt(d)fbzq/bzq] character, with the LUMO delocalized on the adjacent Pt(bzq) fragments. In frozen CH 2 Cl 2 , an additional low-energy shoulder (∼640-675 nm) is also detected, probably due to the presence of close distinct emissive states originating in small modifications in the ground-state structure in frozen solution.

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C–H and P–C(Ph) activation competitive processes caused by interaction with the solvate [cis-Pt(C₆F₅)₂(thf)₂]

Cited by 7 publications

References 92 publications

A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene

A Hydrido η1-Alkynyl Diplatinum Complex Obtained from a Phosphinito Phosphanido Complex and Trimethylsilylacetylene

Bridging and Terminal (Phosphanido)platinum Complexes

Remarkable Influence of the Cyclometalating Ligand on the Nuclearity and Properties of Heterobridged (μ-X)(μ-C≡CR) Platinum(II) Complexes

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