Use of aryltin compounds in the preparation of diaryl- and diaroyl-di-µ-chloro-bis(triorganophosphine)diplatinum(<scp>II</scp>) complexes

Eaborn, Colin; Odell, Kevin J.; Pidcock, Alan

doi:10.1039/dt9780001288

Cited by 38 publications

(8 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The large increase in the direct coupling (J BX ) from ca. 1870 Hz in 16and 17 to more than 5000 Hz in[19] + and[20] + is consistent with P trans to halide; the remarkably high value appears also to be characteristic of halide cis to an aryl or aroyl group in binuclear platinum(II) complexes 33. Treatment of complex 16 with an excess of HCl cleaves both the Pt-Pt and Pt-C bonds giving cis-[PtCl 2 (PPh 3 ) 2 ], but strong acids containing poorly coordinating anions react with 16-18 forming l-hydridodiplatinum(II) cations having an A-frame structure, which are readily identified by 1 H and 31 P NMR spectroscopy.…”

supporting

confidence: 54%

“…In other solvents products having more complex spectra are obtained, which have [19] + and [20] + is consistent with P trans to halide; the remarkably high value appears also to be characteristic of halide cis to an aryl or aroyl group in binuclear platinum(II) complexes. 33 Treatment of complex 16 with an excess of HCl cleaves both the Pt-Pt and Pt-C bonds giving cis-[PtCl 2 (PPh 3 ) 2 ], but strong acids containing poorly coordinating anions react with 16-18 forming l-hydridodiplatinum(II) cations having an A-frame structure, which are readily identified by 1 The Pt-P and P-P coupling constants derived from analysis of the 31 P NMR spectrum of [22] + are given in Table 2. Notable is the magnitude of J PtP , 3701 Hz, to the phosphorus atoms of the PPh 3 ligands, which are trans to the bridging hydride in an ideal A-frame structure, cf.…”

Section: Formation and Reactions Of Diplatinum(i) Complexesmentioning

confidence: 99%

See 1 more Smart Citation

ortho-Metallated complexes of platinum(ii) and diplatinum(i) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

et al. 2007

View full text Add to dashboard Cite

When the ortho-metallated complexes cis-[Pt(kappa(2)-C6H3-5-R-2-PPh2)2] (R = H 1, Me 2) are either heated in toluene or treated with CO at room temperature, one of the four-membered chelate rings is opened irreversibly to give dinuclear isomers [Pt2(kappa(2)-C6H3-5-R-2-PPh2)2(mu-C6H3-5-R-2-PPh2)2] (R = H 10, Me 11). A single-crystal X-ray diffraction study shows the Pt...Pt separation in 10 to be 3.3875(4) A. By-products of the reactions of 1 and 2 with CO are polymeric isomers (R = H 13, Me 14) in which one of the P-C ligands is believed to bridge adjacent platinum atoms intermolecularly. In contrast to the behaviour of 1 and 2, when cis-[Pt(kappa(2)-C6H3-6-Me-2-PPh2)2] (cis-3) is heated in toluene, the main product is trans-3, and reaction of cis-3 with CO gives a carbonyl complex [Pt(CO)(kappa(1)-C-C6H3-6-Me-2-PPh2)(2-C6H3-6-Me-2-PPh2)] 15, in which one of the carbanions is coordinated only through the carbon. Formation of a dimer analogous to 10 or 11 is sterically hindered by the 6-methyl substituent. Comproportionation of 1 or 2 with [Pt(PPh3)2L] (L = PPh3, C2H4) gives diplatinum(I) complexes [Pt2(mu-C6H3-5-R-2-PPh2)2(PPh3)2] (R = H 16, Me 17). An X-ray diffraction study shows that 17 contains a pair of planar-coordinated metal atoms separated by 2.61762(16) A. There is no evidence for the formation of an analogue containing mu-C6H3-6-Me-2-PPh2. The axial PPh3 ligands of 16 are readily replaced by ButNC giving [Pt2(mu-2-C6H4PPh2)2(CNBut)2] 18, which is protonated by HBF4 to form a mu-hydridodiplatinum(II) salt [Pt2(mu-H)(mu-2-C6H4PPh2)2(CNBut)2]BF4 [21]BF4. The J(PtPt) values in [21]BF4 and 18, 2700 Hz and 4421 Hz, respectively, reflect the weakening of the Pt-Pt interaction caused by protonation. Similarly, 16 and 17 react with the electrophiles iodine and strong acids to give salts of general formula [Pt2(mu-Z)(mu-C6H3-5-R-2-PPh2)2(PPh3)2]Y (Y = Z = I, R = H 19+, Me 20+; Z = H, Y = BF4, PF6, OTf, R = H 22+; Z = H, Y = PF6, R = Me 23+). A single-crystal X-ray diffraction study of [23]PF6 shows that the cation has an approximately A-frame geometry, with a Pt-Pt separation of 2.7888(3) A and a Pt-H bond length of 1.62(1) A, and that the 5-methyl substituents have undergone partial exchange with the 4-hydrogen atoms of the PPh2 groups of the bridging carbanion. The latter observation indicates that the added proton of [23]+ undergoes a reversible reductive elimination-oxidative addition sequence with the Pt-C(aryl) bonds.

show abstract

supporting

confidence: 54%

Section: Formation and Reactions Of Diplatinum(i) Complexesmentioning

confidence: 99%

ortho-Metallated complexes of platinum(ii) and diplatinum(i) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

et al. 2007

View full text Add to dashboard Cite

show abstract

“…Precursor-catalyzed isomerization: After carrying out several reactions in different reactant combinations, [42] we found a notable cis to trans conversion only when 4 a was treated with a stoichiometric amount of [43] The interaction between the two fragments takes place through the binding of the platinum to the alkyne in an h 2 fashion and additional support may be provided through a Pt-Pt interaction. Binuclear complexes showing similar kinds of interactions have been reported previously.…”

Section: Mechanistic Investigationsmentioning

confidence: 99%

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

Zhang

Blacque

Venkatesan

2013

Chemistry A European J

View full text Add to dashboard Cite

We have synthesized cis and trans N-heterocyclic carbene (NHC) platinum(II) complexes bearing σ-alkynyl ancillary ligands, namely [Pt(dbim)2 (CCR)2 ] [DBIM=N,N'-didodecylbenzimidazoline-2-ylidene; R=C6 H4 F (4), C6 H5 (5), C6 H2 (OMe)3 (6), C4 H3 S (7), and C6 H4 CCC6 H5 (8)] and [Pt(ibim)2 (CCC6 H5 )2 ] (9) (ibim=N,N'-diisopropylbenzimidazoline-2-ylidene), starting from [Pt(cod)(CCR)2 ] (COD=cyclooctadiene) and 2 equivalents of [dbimH]Br ([ibimH]Br for complexes 9) in the presence of tBuOK and THF. Mechanistic investigations aimed at uncovering the cis to trans isomerization reaction have been performed on the representative cis complex 5 a [Pt(dbim)2 (CCC6 H5 )2 ] and revealed the isomerization to progress smoothly in good yield when 5 a was treated with catalytic amounts of [Pt(cod)(CCR)2 ] at 75 °C in THF or when 5 a was heated at 200 °C in the solid state under an inert atmosphere. Detailed examination of the reactions points to the possible involvement, in a catalytic fashion, of a solvent-stabilized Pt(II) dialkyne complex in the former case and a Pt(0) NHC complex in the latter case, for the transformation of the cis isomer to the corresponding trans complex. Thermal stability and the isomerization process in the solid state have been further investigated on the basis of TGA and DSC measurements. X-ray diffraction studies have been carried out to confirm the solid-state structures of 4 b, 5 a, 5 b, and 9 b. All of the synthesized dialkyne complexes 4-9 exhibit phosphorescence in solution, in the solid state at room temperature (RT), and also in frozen solvent glasses at 77 K. The emission wavelengths and quantum yields have been found to be highly tunable as a function of the alkynyl ligand. In particular, the trans isomer of complex 9 in a spin-coated film (10 wt % in poly(methyl methacrylate), PMMA) exhibits a high phosphorescence quantum yield of 80 %, which is the highest reported for Pt(II) -based deep-blue emitters. Experimental observations and time-dependent density functional theory (TD-DFT) calculations are strongly indicative of the emission being mainly governed by metal-perturbed interligand ((3) IL) charge transfer.

show abstract

“…17.5 ppm. The 1 J PPt coupling constants are characteristic for Pt(II) compounds with a carbon atom trans to a phosphorus (from 1773 to 1881 Hz) [24] or to a chloride (4713.0 Hz) [22,25] atom.…”

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 99%

Cyclometallated platinum(II) complexes containing the chiral ligand [2-(diphenyl-phosphanyl)-benzylidene]-(1-phenyl-ethyl)-amine: Synthesis and molecular structures of the compounds [PtCl(Me){κ2-(R)-Ph2P(C6H4)CHNCH(Ph)Me-P,N}] and [Pt{κ3-(S)-Ph2P(C6H4)CHNCH(C6H4)Me-P,N,C}Py]BF4

Ramírez

Contreras

Valderrama

et al. 2008

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Use of aryltin compounds in the preparation of diaryl- and diaroyl-di-µ-chloro-bis(triorganophosphine)diplatinum(II) complexes

Cited by 38 publications

References 0 publications

ortho-Metallated complexes of platinum(ii) and diplatinum(i) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

ortho-Metallated complexes of platinum(ii) and diplatinum(i) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

Cyclometallated platinum(II) complexes containing the chiral ligand [2-(diphenyl-phosphanyl)-benzylidene]-(1-phenyl-ethyl)-amine: Synthesis and molecular structures of the compounds [PtCl(Me){κ2-(R)-Ph2P(C6H4)CHNCH(Ph)Me-P,N}] and [Pt{κ3-(S)-Ph2P(C6H4)CHNCH(C6H4)Me-P,N,C}Py]BF4

Contact Info

Product

Resources

About

Use of aryltin compounds in the preparation of diaryl- and diaroyl-di-µ-chloro-bis(triorganophosphine)diplatinum(II) complexes

Cited by 38 publications

References 0 publications

ortho-Metallated complexes of platinum(ii) and diplatinum(i) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

ortho-Metallated complexes of platinum(ii) and diplatinum(i) containing the carbanions (2-diphenylphosphino)phenyl and (2-diphenylphosphino)-n-tolyl (n = 5, 6)

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene PtII Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

Cyclometallated platinum(II) complexes containing the chiral ligand [2-(diphenyl-phosphanyl)-benzylidene]-(1-phenyl-ethyl)-amine: Synthesis and molecular structures of the compounds [PtCl(Me){κ2-(R)-Ph2P(C6H4)CHNCH(Ph)Me-P,N}] and [Pt{κ3-(S)-Ph2P(C6H4)CHNCH(C6H4)Me-P,N,C}Py]BF4

Contact Info

Product

Resources

About

Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies