Absorption spectroscopy of (Ind)Ni(PPh<sub>3</sub>)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)<sub>2</sub> (M = Ni, Ru; Ind = indenyl)

Bayrakdarian, Malken; Davis, Martin J.; Reber, Christian; Zargarian, Davit

doi:10.1139/v96-246

Cited by 16 publications

(8 citation statements)

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“…, Ni−C1 > Ni−C2 > Ni−C3). Such nonsymmetrical Ni−Ind interactions, which seem to result in a “tilting” of the indenyl ligand, have also been observed in 1 5c and the related complex (Ind)Ni(PPh 3 )Cl 5a. In the latter compounds, this “sideways slippage” has been shown to be caused by the unequal trans influences of the pseudo-trans ligands PPh 3 and Cl.…”

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confidence: 79%

“…When equimolar quantities of (1-Me-Ind)Ni(PPh 3 )Cl, 1 , AgBF 4 , and PPh 3 are stirred in CH 2 Cl 2 , the bis(phosphine) cationic species [(1-Me-Ind)Ni(PPh 3 ) 2 ] + , 2 , is obtained in 90% yield (eq 1). This methodology can also be used to prepare cationic complexes bearing different phosphine ligands, such as [(1-Me-Ind)Ni(PPh 3 )(PMe 3 )] + , 3 .…”

mentioning

confidence: 73%

“…Thus, the presence of a positive charge on certain transition metal complexes seems to confer to these species interesting patterns of reactivity. In conjunction with our ongoing investigations into the chemistry of neutral nickel indenyl complexes, we were interested in studying the influence of a positive charge on the structural features and reactivities of these compounds. Although cationic Cp complexes of nickel have been reported, little is known about their structural features and reactivities with olefins.…”

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confidence: 99%

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Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺

1997

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Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺

1997

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“…Unless otherwise stated, the 1 H (400 MHz), 13 C{ 1 H} (100.56 and 75.44 MHz), and 31 P{ 1 H} (161.92 MHz) NMR spectra were recorded at ambient temperature; the IR spectra were recorded as KBr pellets. The Ni−Cl precursors IndNi(PPh 3 )Cl ( 1 ) and (1-Me-Ind)Ni(PPh 3 )Cl ( 2) were prepared as described elsewhere. 4a,b …”

Section: Methodsmentioning

confidence: 99%

“…We became interested in the role played by X→M π-interactions during our studies on the structures and reactivities of the indenylnickel complexes [(1-R‘-Ind)Ni(PPh 3 )(X)] n + (Ind = indenyl; R‘ = H and Me, X = Cl and Me, with n = 0; X = PPh 3 , PMe 3 , and MeCN with n = 1 5 ), including their catalytic activities in the dehydropolymerization of PhSiH 3 . Some of our initial results indicated that the equilibrium stabilities of (Ind)Ni(PPh 3 )(halides) follows the order I > Br > Cl, while the Ni−F derivative could not be prepared .…”

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Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

et al. 1998

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The complex (1-Me-indenyl)Ni(PPh3)(phthalimidate) has been prepared and fully characterized by IR and 1H, 13C{1H}, and 31P{1H} NMR spectroscopy and single-crystal X-ray diffraction. The analogous 4,5-dichlorophthalimidato, maleimidato, and succinimidato complexes have also been prepared and characterized spectroscopically. These complexes are thermally stable, in contrast to the analogous Ni−amido species, which could not be prepared. Reactivity studies have shown that the Ni−imidato bond is fairly unreactive in insertion and nucleophilic reactions, and VT 1H NMR studies suggest that the rotation around the Ni−N bond in the maleimidato complex is hindered by ca. 11 kcal/mol. The solid-state structure of the phthalimidato derivative showed that the P, N, C1, and C3 atoms are arranged around the Ni atom in a distorted-square-planar coordination environment, while the C2 atom is within bonding distance above the main square plane. The phthalimidato ligand is η1(N)-coordinated to Ni; the Ni−N bond is relatively short (1.895(4) Å), and the orientation of the imidato ligand is such that the planes bearing the atoms P, Ni, N and C9, N, C16 are rotated by ca. 76° with respect to each other. The hapticity of the indenyl ligand is characterized by an allyl-ene distortion (η5↔η3) and a partial localization of bonding inside the indenyl ring (η3↔η1,η2). 1H and 13C{1H} NMR spectra indicate that the nonsymmetrical coordination of the indenyl ligand, which can be attributed to the different trans influences of the phthalimidato and PPh3 ligands, is maintained in the solution. The character of the Ni−imidato bond has been discussed in terms of electrostatic-covalent and π-bonding interactions.

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Nickel: Organometallic ChemistryBased in part on the article Nickel: Organometallic Chemistry by Clifford P. Kubiak which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Zargarian

2005

Encyclopedia of Inorganic Chemistry

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The organometallic chemistry of nickel has experienced rapid growth over the past decade. A number of exciting new areas have emerged, such as the reactivities of Ni(0)‐carbene complexes and the polymerization of olefins catalyzed by nickel complexes of nitrogen‐based ligands. In addition, the traditionally rich area of Ni‐catalyzed organic transformations has undergone major developments that have expanded the scope of their applications. These are the subjects of the present chapter. Among the topics that will be discussed are the preparation, characterization, and reactivity studies of nickel complexes of allyl, cyclopentadienly, indenyl, and tris(pyrazolyl)borate ligands. The main structural and bonding properties of these complexes are presented and their major reactivities are outlined. Another topic of importance is the chemistry of the nickel complexes of hydride, alkyl, alkenyl, and silyl ligands. Hydrido and alkyl complexes of nickel are often involved in many catalytic processes of commercial importance, and so an in‐depth understanding of the fundamental reactivities of these complexes is crucial to expanding their practical applications. Silyl complexes are involved in the transformations of organosilicon compounds, and for this reason their basic reactivities and structural properties are of interest. Zerovalent nickel complexes are also very important in the catalytic organic transformations. One of the most exciting developments in this area is the recent introduction of N‐heterocyclic carbene ligands. Ni complexes of these ligands have been shown to be important catalysts and reagents for a number of important organic transformations. Some of the practical methods for preparing Ni‐carbene complexes will be outlined, and the recently reported catalytic reactions promoted by these complexes will be described. One of the most important areas of growth for the chemistry of nickel has been the polymerization and copolymerization of olefins. Thus, this chapter will describe the discovery of a family of diimine complexes that catalyze the polymerization of aliphatic olefins. A series of new and highly efficient catalysts were introduced in rapid progression, a great deal of new chemistry has been discovered, and a number of industrial processes have been developed on the basis of these nickel complexes. We will also discuss the emergence of new strategies for the efficient cross‐coupling of alkyl halides with organozinc and Grignard reagents, as well as the coupling of dienes with CO 2 .

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Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Cited by 16 publications

References 24 publications

Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺

Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺

Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

Nickel: Organometallic ChemistryBased in part on the article Nickel: Organometallic Chemistry by Clifford P. Kubiak which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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Absorption spectroscopy of (Ind)Ni(PPh3)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)2 (M = Ni, Ru; Ind = indenyl)

Cited by 16 publications

References 24 publications

Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]+

Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]+

Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

Nickel: Organometallic ChemistryBased in part on the article Nickel: Organometallic Chemistry by Clifford P. Kubiak which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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Product

Resources

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Absorption spectroscopy of (Ind)Ni(PPh₃)X (Ind = indenyl, 1-Me-indenyl; X = Cl, Br, Me) and M(Ind)₂ (M = Ni, Ru; Ind = indenyl)

Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺

Preparation and Characterization of Cationic Nickel Indenyl Complexes [(1-methylindenyl)NiLL‘]⁺