Cyclometalation of the platinum metals with nitrogen and alkyl, alkenyl, and benzyl carbon donors

Newkome, George R.; Puckett, Wallace E.; Gupta, Vinod K.; Kiefer, Garry E.

doi:10.1021/cr00072a006

Cited by 401 publications

(157 citation statements)

References 63 publications

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“…The two platinum atoms are essentially squareplanar coordinated with slight square-pyramidal distortions. For Pt(1) the maximum distances from the best plane are ϩ0.041(1) and Ϫ0.055(4) Å for Pt (1) and N(2), respectively. For Pt(2) the maximum distances from the best plane are ϩ0.017(1) and Ϫ0.021(3) Å for Pt (2) and N(1), respectively.…”

Section: Reaction With Acidsmentioning

confidence: 98%

Dinuclear, Tricyclometallated Platinum(II) Derivatives − Substitution Reactions and Reactivity of the Platinum−Carbon Bonds

et al. 2004

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In the recently reported dinuclear cyclometallated species [Pt 2 (R)(L)(DMSO) 2 ] [H 3 L = 6-phenyl-2,2Ј-bipyridine; R = Me (1a), Ph (1b)] the threefold deprotonated ligand L links the two platinum atoms acting as an NЈ,C(3) and a C,N,C donor. Aspects of their reactivity have been studied first with regards to the substitution of the two DMSO ligands, which are coordinated to the platinum atom trans to a nitrogen and a carbon atom, respectively. Substitution of DMSO with neutral two-electron donors affords several new species, all having the same bridging ligand L: [Pt 2 (R)(L)(LЈ) 2 ] [LЈ = PPh 3 (2a, 2b), CO (3a, 3b)] and [Pt 2 (R)(L)(LЈ)(DMSO)] [LЈ =3,5-Me 2 -py (4a)]. The potentially bidentate diphosphane Ph 2 P(CH 2 ) 3 PPh 2 (dppp) gives a more complex species having both chelating and bridging dppp ligands [{Pt(Me)(L)(dppp)} 2 (µ-dppp)] (5a). The reactivity of the platinum−carbon bonds with HCl has been studied in complexes 1a, 1b and 2a, 2b and found to be strongly dependent on the nature of the ancillary ligands. To discern the most labile of the four metal−carbon bonds, the reaction has been

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Section: Reaction With Acidsmentioning

confidence: 98%

Dinuclear, Tricyclometallated Platinum(II) Derivatives − Substitution Reactions and Reactivity of the Platinum−Carbon Bonds

et al. 2004

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“…9) exist, i.e. bidentate N,C(3)-coordination (23), monodentate N-coordination (24), monodentate, covalent M-C(3) linkage (25) and bidentate N,S-coordination (26 126 the latter compound is an especially interesting example because it combines both motifs 23 and 24 within one single complex.…”

Section: -(2-thienyl)pyridinesmentioning

confidence: 99%

“…Common to the otherwise different approaches, such as directed ortho-metalation, 4 remote functionalization, [5][6][7][8][9][10][11][12][13][14] or cyclometalation, [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] is the precoordination of the substrate to a metal center, followed by the activation of geometrically accessible C-H bonds, which can be adjacent or remote, to generate a template for further functionalization. In particular, cyclometalation has attracted much attention and, not surprisingly, formed the subject of several review articles.…”

Section: Introductionmentioning

confidence: 99%

“Rollover” cyclometalation – early history, recent developments, mechanistic insights and application aspects

2012

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''Rollover'' cyclometalation constitutes a special case among the well-known class of cyclometalation reactions. An overview is given that covers the very first description of this reaction type, as well as recent developments. In addition, not only condensed-phase experiments are reviewed, but also investigations based on mass spectrometric techniques, together with ''in silico'' studies using DFTbased calculations are considered. While the latter two methods allow for a detailed analysis of the intrinsic factors that affect the reaction mechanisms, consideration of all three regimes permits to develop a coherent mechanistic picture and to address the often noted gap between condensed-and gasphase studies. Moreover, the quite unexpected reactivity of ''rollover'' cyclometalated complexes in gasphase experiments, as well as potential applications, e.g. in synthetic procedures, are discussed in some detail.

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“…(J Am Soc Mass Spectrom 2010, 21, 1265-1274) © 2010 American Society for Mass Spectrometry C yclometalation occurs when a ligand on an organo-metal complex undergoes an intramolecular metalation with concomitant formation of a chelate ring containing a metal-carbon bond [1]. This kind of transformation has attracted significant attention over the past three decades [2][3][4][5][6][7]. On the one hand, cyclometalation can be detrimental to a desired reaction course and can be prevented by a variety of techniques to improve catalytic efficiency of the metal complex.…”

mentioning

confidence: 99%

“…This kind of transformation has attracted significant attention over the past three decades [2][3][4][5][6][7]. On the one hand, cyclometalation can be detrimental to a desired reaction course and can be prevented by a variety of techniques to improve catalytic efficiency of the metal complex.…”

mentioning

confidence: 99%

Studies on gas-phase cyclometalations of [ArNi(PPh₃)n]⁺ (n = 1 or 2) by electrospray ionization tandem mass spectrometry

Zhou

Zhao

Chen

et al. 2010

J. Am. Soc. Mass Spectrom.

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Gas-phase cyclometalation of [ArNi(PPh 3 ) n ] ϩ (n ϭ 1, 2) complexes have been studied by ESI-MS/MS. The electron-donating substituents of aromatic iodides in the para position were found to inhibit the cyclometalation process of losing ArH, while the electron-withdrawing substituents in the para position were found to enhance it. These results indicate that the cyclometalation process of losing ArH is favored by electron-deficient aromatic groups. In addition, the detailed dissociation pathways of the cationic nickel complexes were studied, and among these pathways, the process of aryl-aryl interchange was also found to proceed in ESI-MS/MS. (J Am Soc Mass Spectrom 2010, 21, 1265-1274) © 2010 American Society for Mass Spectrometry C yclometalation occurs when a ligand on an organo-metal complex undergoes an intramolecular metalation with concomitant formation of a chelate ring containing a metal-carbon bond [1]. This kind of transformation has attracted significant attention over the past three decades [2][3][4][5][6][7]. On the one hand, cyclometalation can be detrimental to a desired reaction course and can be prevented by a variety of techniques to improve catalytic efficiency of the metal complex. As cyclometalation methodology has been developed, a number of cyclometalated complexes were employed successfully in organic synthesis [8,9], catalysis [10 -12], and photochemistry [13][14][15]. Mechanisms for the cyclometalation associated with C-H bond cleavage have been proposed [16 -21], and three related mechanisms for C-H bond cleavage are typically accepted: oxidative addition, electrophilic substitution, and multicentered pathways (such as -bond metathesis) [22][23][24][25][26]. The actual mechanisms that pertain for cyclometalation of a given metal complex are highly dependent on the exact nature of the metal complexes, identities of hydrocarbon substituents, solvents involved, and specific operating conditions [21]. As a result, a complete understanding and description of the general mechanism are still lacking, and more data are needed before we can fully describe critical reactivity patterns.The focus to date has been on the study of solutionphase cyclometalations, but gas-phase cyclometalations have recently received more attention [27][28][29]. Generally, gas-phase studies conducted with tandem mass spectrometry (MS/MS) on extremely small sample quantities can theoretically ascertain the propensity for a complex to undergo certain kinds of reactions. The energy conditions and dissociation pathways provide useful insights, with applicability to related solutionphase reactions [30 -40]. Based on the gas-phase methodologies, Henderson and coworkers published their investigation of the cyclometalation of palladium(II) and platinum(II) diphosphine complexes MCl 2 (Ph 2 P (CH 2 ) 5 PPh 2 ) in 2004 [28]. More recently, Schwarz and coworkers explored the whole process of cyclometalation of 2,2=-bipyridine platinum(II) complexes in gas phase by a combination of gas-phase methodologies and theoretical calcu...

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Cyclometalation of the platinum metals with nitrogen and alkyl, alkenyl, and benzyl carbon donors

Cited by 401 publications

References 63 publications

Dinuclear, Tricyclometallated Platinum(II) Derivatives − Substitution Reactions and Reactivity of the Platinum−Carbon Bonds

Dinuclear, Tricyclometallated Platinum(II) Derivatives − Substitution Reactions and Reactivity of the Platinum−Carbon Bonds

“Rollover” cyclometalation – early history, recent developments, mechanistic insights and application aspects

Studies on gas-phase cyclometalations of [ArNi(PPh₃)n]⁺ (n = 1 or 2) by electrospray ionization tandem mass spectrometry

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Cyclometalation of the platinum metals with nitrogen and alkyl, alkenyl, and benzyl carbon donors

Cited by 401 publications

References 63 publications

Dinuclear, Tricyclometallated Platinum(II) Derivatives − Substitution Reactions and Reactivity of the Platinum−Carbon Bonds

Dinuclear, Tricyclometallated Platinum(II) Derivatives − Substitution Reactions and Reactivity of the Platinum−Carbon Bonds

“Rollover” cyclometalation – early history, recent developments, mechanistic insights and application aspects

Studies on gas-phase cyclometalations of [ArNi(PPh3)n]+ (n = 1 or 2) by electrospray ionization tandem mass spectrometry

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Studies on gas-phase cyclometalations of [ArNi(PPh₃)n]⁺ (n = 1 or 2) by electrospray ionization tandem mass spectrometry