Overcrowded Organometallic Platinum(II) Complexes That Behave as Molecular Gears

Romeo, Raffaello; Carnabuci, Salvatore; Fenech, Lucia; Plutino, Maria Rosaria; Albinati, Alberto

doi:10.1002/ange.200600827

Cited by 10 publications

(7 citation statements)

References 22 publications

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“…For the latter scenario, 14-electron T-shaped species involving phosphine ligands can be envisaged as feasible intermediates. The dissociative pathway fully prevails when overcrowded PR 3 ligands are employed, where R stands for o -methoxyphenyl 11 [110] and o -tolyl 12 [111]. The detailed mechanism (Scheme 11) is described as follows: (i) dissociative nitrogen decomplexation, (ii) isomerization between two nonequivalent exchanging sites, and (iii) nitrogen coordination recovering the initial chelating situation.…”

Section: Reviewmentioning

confidence: 99%

“…Concerning 14-electron intermediates b and b’ , the assistance of methoxy groups in 11b , b’ [110] as well as the presence of agostic interactions in 12b , b’ [111] can be postulated (Fig. 16).…”

Section: Reviewmentioning

confidence: 99%

“…Feasible interactions for unsaturated intermediates 11b (left) and 12b (right) during fluxional motions [110–111]. …”

Section: Reviewmentioning

confidence: 99%

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True and masked three-coordinate T-shaped platinum(II) intermediates

Ortuño¹,

Conejero²,

Lledós³

2013

Beilstein J. Org. Chem.

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SummaryAlthough four-coordinate square-planar geometries, with a formally 16-electron counting, are absolutely dominant in isolated Pt(II) complexes, three-coordinate, 14-electron Pt(II) complexes are believed to be key intermediates in a number of platinum-mediated organometallic transformations. Although very few authenticated three-coordinate Pt(II) complexes have been characterized, a much larger number of complexes can be described as operationally three-coordinate in a kinetic sense. In these compounds, which we have called masked T-shaped complexes, the fourth position is occupied by a very weak ligand (agostic bond, solvent molecule or counteranion), which can be easily displaced. This review summarizes the structural features of the true and masked T-shaped Pt(II) complexes reported so far and describes synthetic strategies employed for their formation. Moreover, recent experimental and theoretical reports are analyzed, which suggest the involvement of such intermediates in reaction mechanisms, particularly C–H bond-activation processes.

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Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

See 1 more Smart Citation

True and masked three-coordinate T-shaped platinum(II) intermediates

Ortuño¹,

Conejero²,

Lledós³

2013

Beilstein J. Org. Chem.

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“…Platinum(II) complexes of the type cis ‐[PtMe 2 (Me 2 SO) 2 ] ( Pt1 )11 and trans ‐[PtMeCl(Me 2 SO) 2 ] ( Pt2 )12 have been employed as useful synthons for introducing the fragments {PtMe 2 } and {PtMeCl}, respectively, into different monocoordinating or chelating heterocyclic systems 12a,12c,14. We thought it worthwhile to extend this methodology to the coordination of the sulfinyl sulfur and pyridinyl nitrogen atoms of compound 9 and tripodal species 6 .…”

Section: Resultsmentioning

confidence: 99%

Mono‐ and Trinuclear Tripodal Platinum(II) Chelated Complexes Containing a Pyridine/Sulfoxide Based Anchoring Framework

et al. 2013

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New tripodal ligands 2,4,6-triethyl-1,3,5-tris{[1-(2-pyridinyl)ethenyl]sulfinylmethyl}benzenes 6, characterized by three pendant chains each containing both sulfoxide and pyridine moieties, were synthesized from the corresponding sulfenic acid and 2-ethynylpyridine. Two diastereomeric mixtures were obtained and separated, one racemic mixture 6a, having a C 3 symmetry axis and the other 6b with no symmetry. With the aim of studying the coordination ability of these chelating-κN,κS type ligands, monobranched racemic [1-(2pyridinyl)ethenyl]sulfinylbenzene 9 was also synthesized. Upon addition of an equivalent amount of the monochelating ligand 9 or the tripodal species 6a to a CD 3 CN solution of a platinum(II) complex of the type cis-[PtMe 2 (Me 2 SO) 2 ] (Pt1) or [a]

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“…Correlated rotations in other organometallic compounds have been investigated [20] and the rotation of a ligand around Pt(II) by associative or dissociative mechanisms has been described [21]. A rack-and-pinion device for which a scanning tunneling microscopy (STM) tip drives a single pinion molecule at low temperature has been recently reported [22].…”

Section: Gearsmentioning

confidence: 99%