Trifluorophosphine Complexes of Nickel

Clark, Ronald J.; Brimm, E. O.

doi:10.1021/ic50027a011

Cited by 36 publications

(5 citation statements)

References 3 publications

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“…The Ni(PF 3 )(CO) 3 complex was first synthesized by Clark and Brimm . However, it apparently has not yet been structurally characterized by X-ray diffraction.…”

Section: Resultsmentioning

confidence: 99%

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Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF₃Metal Carbonyls of the First Row Transition Metals

Deng

Wang²,

Li³

et al. 2011

Inorg. Chem.

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The variety of known very stable PF(3) metal derivatives analogous to metal carbonyls suggests the synthesis of SF(3) metal derivatives analogous to metal nitrosyls. However, the only known SF(3) metal complex is the structurally uncharacterized (Et(3)P)(2)Ir(CO)(Cl)(F)(SF(3)) synthesized by Cockman, Ebsworth, and Holloway in 1987 and suggested by electron counting to have a one-electron donor SF(3) group rather than a three-electron donor SF(3) group. In this connection, the possibility of synthesizing SF(3) metal derivatives analogous to metal nitrosyls has been investigated using density functional theory. The [M]SF(3) derivatives with [M] = V(CO)(5), Mn(CO)(4), Co(CO)(3), Ir(CO)(3), (C(5)H(5))Cr(CO)(2), (C(5)H(5))Fe(CO), and (C(5)H(5))Ni analogous to known metal nitrosyl derivatives are all predicted to be thermodynamically disfavored with respect to the corresponding [M](SF(2))(F) derivatives by energies ranging from 19.5 kcal/mol for Mn(SF(3))(CO)(4) to 5.4 kcal/mol for Co(SF(3))(CO)(3). By contrast, the isoelectronic [M]PF(3) derivatives with [M] = Cr(CO)(5), Fe(CO)(4), Ni(CO)(3), (C(5)H(5))Mn(CO)(2), (C(5)H(5))Co(CO), and (C(5)H(5))Cu are all very strongly thermodynamically favored with respect to the corresponding [M](PF(2))(F) derivatives by energies ranging from 64.3 kcal/mol for Cr(PF(3))(CO)(5) to 31.6 kcal/mol for (C(5)H(5))Co(PF(3))(CO). The known six-coordinate (Et(3)P)(2)Ir(CO)(Cl)(F)(SF(3)) is also predicted to be stable relative to the seven-coordinate (Et(3)P)(2)Ir(CO)(Cl)(F)(2)(SF(2)). Most of the metal SF(3) complexes found in this work are singlet structures containing three-electron donor SF(3) ligands with tetrahedral sulfur coordination. However, two examples of triplet spin state metal SF(3) complexes, namely, the lowest energy (C(5)H(5))Fe(SF(3))(CO) structure and a higher energy Co(SF(3))(CO)(3) structure, are found containing one-electron donor SF(3) ligands with pseudo square pyramidal sulfur coordination with a stereochemically active lone electron pair.

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“…The Ni(PF 3 )(CO) 3 complex was first synthesized by Clark and Brimm . However, it apparently has not yet been structurally characterized by X-ray diffraction.…”

Section: Resultsmentioning

confidence: 99%

“…The Ni(PF 3 )-(CO) 3 complex was first synthesized by Clark and Brimm. 53 However, it apparently has not yet been structurally characterized by X-ray diffraction. Our optimized geometry of Ni(PF 3 )-(CO) 3 constrained to C 3v symmetry led to structure Ni-1S (Figure 10 and Table 11).…”

Section: M(pf 3 )(Co)mentioning

confidence: 99%

Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF₃Metal Carbonyls of the First Row Transition Metals

Deng

Wang²,

Li³

et al. 2011

Inorg. Chem.

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“…The evaluation of the experimental results and the postulation of reaction mechanisms can be attempted by recognizing; (1) No compounds are formed which contain both silicon and phosphorus, thus eliminating the reaction R3SiN3 + R3_zPCh -> R3SiN=PR3_*Ch + N2 (2) The exchange of the halogen and azido moiety is complete, even in the case of the polyhalophosphines, where multiple exchange can and did occur.…”

Section: Discussionmentioning

confidence: 99%

“…The desired product was a N-triorganosilylchlorophosphineimine, which in analogy to diphenylphosphinyl azide was supposed to be investigated as a chain-terminating group in the preparation of linear phosphonitriles.10 Experimental All reactions were conducted either in a nitrogen atmosphere or in a vacuum system with rigid exclusion of moisture and oxygen. Caution should be exercised during the initial stages (1) Presented in part before the Division of Inorganic Chemistry, 148th National Meeting of the American Chemical Society, Chicago, 111., Sept.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Chlorophosphines with Silyl Azides

Kratzer¹,

Paciorek²

1965

Inorg. Chem.

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“…On the other hand, the examination of the force constants in the series Ni(CO)4_"(PF3)n (n = 0, 1, 2, 3, and 4) indi cates that PF3 has about the same properties as CO (59,123). This is supported also by the statistical distribution of the products in the ex change reaction between Ni(CO)4 and PF3 and by the little variation of 31 P NMR chemical shift on these products (56). Loutellier and Bigorgne (123) prefer to consider trifluorophosphine as a weak a donor and weak w acceptor for the following reasons.…”

Section: Polymerization and Cyclization Of Alkynesmentioning

confidence: 92%

Chemistry of Zerovalent Nickel, Palladium, and Platinum Derivatives

Malatesta¹,

Ugo²,

Cenini³

1967

Werner Centennial

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The chemistry of the zerovalent state in nickel, palladium, and platinum compounds is reviewed. After a historical introduction in which the development of this chemistry is analyzed in terms of the current theory of the stabilization of low valency states, the most interesting classes of zero valent compounds are described. The stability and properties of these compounds are discussed and related to the nature of the ligands and the coordinated metal. The catalytic properties of these zerovalent derivatives toward olefins, diolefins, and acetylenes are considered in connection with the facility of ligands exchange, the varia tion of coordination number, and the stereochemistry. A discussion of the π bond is reported.'he first coordination compound with a low oxidation number, tetracarbonylnickel (HI), was discovered in 1890. Despite extensive efforts, however, very few substances of this type were synthesized in the next 50 years.The lack of any knowledge on the structure and bonds of these com pounds was responsible for the poor results. In fact, when tetracarbonylnickel was first prepared, Werner's theory had not as yet been postulated, and even later the theory was not extended to the carbonyls because they were considered anomalous compounds, owing to their chemical and physical properties.The studies on coordination compounds with the central metal in a low oxidation state began to fluorish just prior to World War II. Nickel, palladium, and platinum were particularly investigated for the following reasons:318

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Trifluorophosphine Complexes of Nickel

Cited by 36 publications

References 3 publications

Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF₃Metal Carbonyls of the First Row Transition Metals

Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF₃Metal Carbonyls of the First Row Transition Metals

Reactions of Chlorophosphines with Silyl Azides

Chemistry of Zerovalent Nickel, Palladium, and Platinum Derivatives

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Trifluorophosphine Complexes of Nickel

Cited by 36 publications

References 3 publications

Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF3Metal Carbonyls of the First Row Transition Metals

Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF3Metal Carbonyls of the First Row Transition Metals

Reactions of Chlorophosphines with Silyl Azides

Chemistry of Zerovalent Nickel, Palladium, and Platinum Derivatives

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Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF₃Metal Carbonyls of the First Row Transition Metals

Trifluorosulfane Ligand as an Analogue of the Nitrosyl Ligand: Highly Exothermic Fluorine Transfer Reactions from Sulfur to Metal in the Chemistry of SF₃Metal Carbonyls of the First Row Transition Metals