Platinum–phosphine cluster compounds

Glockling, F.; McBride, T.; Pollock, Robert

doi:10.1039/c3973000650a

Cited by 26 publications

(15 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The properties and formation of multinuclear μ-PR 2 structures formed from M(0)-PR 3 precursors have been studied most extensively for platinum but still comparatively little is known regarding the reaction mechanism, which includes the identification of reaction intermediates. As depicted in Scheme , chemoselectivity varies with reaction conditions, and intermediate formation of κ 2 -P,C-chelate M-H complexes through ortho -C–H bond cyclometalation was proposed for Pt − and established for other metals. − In fact, 2-LiC 6 H 4 PPh 2 and derivatives thereof have commonly been used as precursors for the preparation of mononuclear κ 2 -P,C- and dinuclear μ:κ 2 -P,C-chelate compounds of Pt. , …”

Section: Introductionmentioning

confidence: 99%

C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0): Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift Calculations of a μ-Phosphanido Diplatinum(II) Platform

et al. 2020

View full text Add to dashboard Cite

Transition-metal phosphanides M−PR 2 are key intermediates in catalytic C−P bond functionalization. M−PR 2 formation from tertiary phosphines through P−C bond cleavage widens the scope beyond P−H functionalized substrates, but mechanistic understanding of this reaction still is fragmentary. Starting from a defined coordination complex has allowed monitoring the reaction of a Pt-PPh 3 moiety and Pt(0) by NMR spectroscopy. Initial Pt(0) transfer is rate-limiting and leads to products from PPh 3 -borne ortho-C−H and C−P bond cleavage along kinetically distinct pathways. Albeit kinetically favored, the reversibility of C−H bond cleavage eventually leads to thermodynamically preferred C−P bond scission. This pathway affords a robust [Pt(μ-PPh 2 )Pt] core structure whose redox chemistry and reactivity toward external ligands are reported. Organometallic products have been substantiated by a combination of magnetic resonance and absorption spectroscopies, X-ray diffraction, and DFT computations.

show abstract

Section: Introductionmentioning

confidence: 99%

C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0): Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift Calculations of a μ-Phosphanido Diplatinum(II) Platform

et al. 2020

View full text Add to dashboard Cite

show abstract

“…The same empirical formula was assigned to the product of thermal decomposition of [PtPh 2 (PPh 3 ) 2 ]. 7 In this paper we describe a hitherto unreported dinuclear platinum complex, which we identified initially as a by-product of the thermally induced isomerisation of the cyclohexyneplatinum(0) complex [Pt(PPh 3 ) 2 (C 6 H 8 )], first to the η 1 -cyclohex-1-enyl cycloplatinated complex [Pt{C 6 H 4 (PPh 2 )-2}(C 6 H 9 )-(PPh 3 )] and subsequently to the isomeric cyclohex-2-enyl and cyclohex-3-enyl complexes. 14…”

mentioning

confidence: 99%

New dinuclear platinum(I) complex obtained from thermal degradation of platinum(>0>)–triphenylphosphine complexes

Bennett¹,

Berry²,

Dirnberger³

et al. 1998

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

Thermolysis of [Pt(PPh 3 ) 2 (C 2 H 4 )], [Pt(PPh 3 ) 3 ] or of various complexes of the type [Pt(PPh 3 ) 2 (alkyne)] in toluene gave the dinuclear platinum() complex [(Ph 3 P)Pt{µ-C 6 H 4 (PPh 2 )-2}(µ-PPh 2 )Pt(PPh 3 )] in ca. 60% yield as a consequence of both C᎐H and P᎐Ph cleavage of co-ordinated triphenylphosphine. The complex, which has been identified by mass spectrometry, NMR ( 31 P, 195 Pt) spectroscopy and single-crystal X-ray diffraction analysis, is probably identical with some of the compounds formulated in the literature either asThe other product of the reaction is the known trinuclear compound [Pt 3 (µ-PPh 2 ) 3 (Ph)(PPh 3 ) 2 ].

show abstract

“…Complexes 6-9 are generally prepared (in varying yields) from the UV irradiation, pyrolysis or heating solutions of the mononuclear zerovalent compounds Pt(PPh 3 ) 4 and (Ph 3 P) 2 Pt(ethene). [38][39][40][41][42] Although Braunstein and co-workers 43 have commented that the opening of a phosphido bridge is rare, the formation of complexes 6-9 implies that the phosphido bridge in 5 was cleaved to give the mononuclear fragments (Ph 3 P) 2 Pt and (Ph 3 P) 2 PtH which in turn lead to the di-and trinuclear complexes 6-9. The formation of the trinuclear species is an important observation in that we must now consider the possibility that Trogler's catalytic hydration system 2 may have contained trinuclear species.…”

Section: Resultsmentioning

confidence: 99%

Studies towards the catalytic anti-Markovnikov functionalisation of alkenes

Richard

Parkins

2008

New J. Chem.

View full text Add to dashboard Cite

In 1986 Jensen and Trogler reported that a biphasic system containing the mononuclear complex trans-[(Me 3 P) 2 PtHCl] and NaOH catalysed the anti-Markovnikov hydration of 1-hexene to 1-hexanol. The unusual method of preparation could also give rise to dinuclear complexes with bridging hydride ligands. We have tested some dinuclear complexes for catalytic activity and discovered that on heating these yield trinuclear complexes. Using the independently prepared trinuclear complex [(dppe) 3 Pt 3 H 3 ] + , we found that it acted as a catalyst for the reaction between 1-octene and methanol to give 1-methoxyoctane, although the results were somewhat erratic. A cause of the erratic behaviour was found to be the presence of varying amounts of hydroperoxide impurities, which underwent a Hock rearrangement in acidic conditions.

show abstract

Platinum–phosphine cluster compounds

Cited by 26 publications

References 0 publications

C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0): Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift Calculations of a μ-Phosphanido Diplatinum(II) Platform

C–P vs C–H Bond Cleavage of Triphenylphosphine at Platinum(0): Mechanism of Formation, Reactivity, Redox Chemistry, and NMR Chemical Shift Calculations of a μ-Phosphanido Diplatinum(II) Platform

New dinuclear platinum(I) complex obtained from thermal degradation of platinum(>0>)–triphenylphosphine complexes

Studies towards the catalytic anti-Markovnikov functionalisation of alkenes

Contact Info

Product

Resources

About