Synergistic Binding of Both Lewis Acids and Bases to Phosphinidenes

Partyka, David V.; Washington, Marlena P.; Updegraff, James B.; Woloszynek, Robert A.; Protasiewicz, John D.

doi:10.1002/anie.200801741

Cited by 49 publications

(32 citation statements)

References 48 publications

(53 reference statements)

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“…[2][3][4][5] As early as 1973, Dimroth reportedt hat silver and mercury complexes of benzimidazolylphosphamethine cyanines could be isolated as solids. [6] However,u nlike otherl ow-coordinate phosphoruscontaining compounds,s uch as phosphides, [7][8][9][10][11] phospholides, [12,13] phosphinidenes, [14][15][16][17][18][19][20][21][22] phosphinines, [23][24][25][26][27][28][29][30] phosphaalkenes, [31][32][33][34][35] isophosphindoliums [36][37][38][39] and phospheniums, [40][41][42][43][44][45] which have all seen extensive development as ligandso ver the years, the coordinationc hemistry of phosphamethine cyanine cations has remained virtually unexplored since Dimroth's seminalwork.…”

Section: Introductionmentioning

confidence: 99%

Assessing the Ligand Properties of NHC‐Stabilised Phosphorus(I) Cations

Binder

Kosnik

Macdonald

2018

Chemistry A European J

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The isolation and full characterisation of a series of cationic metal-carbonyl complexes bearing an N-heterocyclic carbene stabilised phosphorus(I) ligand are reported. Specifically, the mononuclear coordination complexes [LM(CO) ][BPh ] (M=Cr, Mo, W), [LFe(CO) ][BPh ] and the dinuclear complexes [LMn (CO) ][BPh ] and [LCo (CO) ][BPh ], in which L=[bis(1,3,4,5-tetramethylimidazol-2-ylidene)phosphanide] , have all been isolated in the solid state and structurally confirmed by single-crystal X-ray diffraction. The dicationic platinum complex trans-[L PtCl ][BPh ] is also reported and fully characterised. The donor ability of [L] has been assessed by IR spectroscopy of its metal-carbonyl complexes and by using DFT calculations. The results suggest that [L] is a weak π-acceptor with moderate donor strength and thus it bridges the gap that exists between phosphines and amines in terms of ligand properties. Collectively, these molecules represent the first crystallographically characterised cationic metal-carbonyl derivatives of a P -centred ligand and are a rare collection of cationic metal-carbonyl complexes.

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Section: Introductionmentioning

confidence: 99%

Assessing the Ligand Properties of NHC‐Stabilised Phosphorus(I) Cations

Binder

Kosnik

Macdonald

2018

Chemistry A European J

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“…[21] In addition, these concepts have been further extended to the syntheses of related P I and N I compounds by the groups of Protasiewicz and Alcarazo. [22] Very recently, the first complex in which BH, which is isoelectronic to a naked carbon atom, is stabilized by two carbene ligands in…”

Section: Introductionmentioning

confidence: 99%

Distinguishing Carbones from Allenes by Complexation to AuCl

Esterhuysen

Frenking

2011

Chemistry A European J

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Quantum chemical calculations have been performed for the dicoordinated carbon compounds C(PPh(3))(2), C(NHC(Me))(2), R(2) C=C=CR(2) (R = H, F, NMe(2)), C(3)O(2), C(CN)(2)(-) and N-methyl-substituted N-heterocyclic carbene (NHC(Me)). The geometries of the complexes in which the dicoordinated carbon molecules bind as ligands to one and two AuCl moieties have been optimized and the strength and nature of the metal-ligand interactions in the mono- and diaurated complexes were investigated by means of energy decomposition analysis. The goal of the study is to elucidate the differences in the chemical behavior between carbones, allenes and carbenes. The results show that carbones bind one and two AuCl species in η(1) fashion, whereas allenes bind them in η(2) fashion. Compounds with latent divalent carbon(0) character can coordinate in more than one way, with the dominant mode indicating the degree of carbone or allene character. The calculated structures of the mono- and diaurated tetraaminoallenes (TAAs) reveal that TAAs exhibit a chameleon-like behavior: The bonding situation in the equilibrium structure is best described as allene [(R(2)N)(2)]C=C=C[(NR(2))(2)] in which the central carbon atom is a tetravalent C(IV) species, but the reactivity suggests that TAAs should be considered as divalent C(0) compounds C{C[(NR(2))(2)]}(2), that is, as "hidden" carbones. Carbon suboxide binds one AuCl preferentially in the η(1) mode, whereas the equilibrium structures of the η(1)- and η(2)-bonded diaurated complex are energetically nearly degenerate. The doubly negatively charged isoelectronic carbone C(CN)(2)(2-) binds one and two AuCl very strongly in characteristic η(1) fashion. The N-heterocyclic carbene complex, [NHC(Me)(AuCl)], possesses a high bond dissociation energy (BDE) for the splitting off of AuCl. The diaurated NHC adduct, [NHC(Me)(AuCl)(2)], has two η(1)-bonded AuCl moieties that exhibit aurophilic attraction, which yield a moderate bond strength that might be large enough for synthesizing the complex. The BDE for the second AuCl in [NHC(Me)(AuCl)(2)] is clearly smaller than the values for the second AuCl in doubly aurated carbone complexes.

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“…[1] Other phosphorus ylides II-IV featuring ad ifferent anionic site, with different properties,and therefore different applications, are also well known. [5] Several stable phosphanylidene-phosphoranes IV [6][7][8] have also been used as phosphinidene transfer agents.B oth the strong s-a nd p-donor character of IV make them excellent ligands for transition metals [9] and for the stabilization of low-valent highly reactive species. [3,4] In contrast, the heavier analogues of I,s ila-ylides III,p resent an enhanced silylenoide character with at ransition-metal-like behavior owing to the weak SiÀPinteraction without any SiÀP p-bond character.…”

mentioning

confidence: 99%

“…Particularly,t he nitrogen analogues, phosphazenes II,have attracted significant attention owing to the wide variety of applications as precursors of fireproof polymers [2] and as non-nucleophilic strong bases. [5] Several stable phosphanylidene-phosphoranes IV [6][7][8] have also been used as phosphinidene transfer agents.B oth the strong s-a nd p-donor character of IV make them excellent ligands for transition metals [9] and for the stabilization of low-valent highly reactive species. [5] Several stable phosphanylidene-phosphoranes IV [6][7][8] have also been used as phosphinidene transfer agents.B oth the strong s-a nd p-donor character of IV make them excellent ligands for transition metals [9] and for the stabilization of low-valent highly reactive species.…”

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confidence: 99%

The Lightest Element Phosphoranylidene: NHC‐Supported Cyclic Borylidene–Phosphorane with Significant B=P Character

et al. 2017

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A borylidene-phosphorane, the lightest phosphoranylidene, which is stabilized by an N-heterocyclic carbene ligand, was synthesized and fully characterized. Experimental electron density analysis and DFT calculations indicate an enhanced ylene character (rather than an ylide character) with an exceptionally strong B→P π-back bonding related to the less electronegative boron compared to phosphorus.

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Synergistic Binding of Both Lewis Acids and Bases to Phosphinidenes

Cited by 49 publications

References 48 publications

Assessing the Ligand Properties of NHC‐Stabilised Phosphorus(I) Cations

Assessing the Ligand Properties of NHC‐Stabilised Phosphorus(I) Cations

Distinguishing Carbones from Allenes by Complexation to AuCl

The Lightest Element Phosphoranylidene: NHC‐Supported Cyclic Borylidene–Phosphorane with Significant B=P Character

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