Synthesis of heteronuclear carbonyl-carbide clysters of transition metals via vertex replacement in a metal polyhedron. X-ray crystal structures of the bimetallic tetragonal-pyramidal [Fe4CoC(CO)14]− and the trimetallic octahedral Fe4CoRhC(CO)16 clusters

Lopatin, V. E.; Губин, С. П.; Mikova, Nadezhda M.; Tsybenov, M.Ts.; Slovokhotov, Yu.L.; Struchkov, Yu. T.

doi:10.1016/0022-328x(85)87344-7

Cited by 23 publications

(4 citation statements)

References 7 publications

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“…However, since the carbonyl bridging the M(2)−M(3) edge is semibridging (M(2)−C(11) = 2.132(5) Å vs M(3)−C(11) = 2.216(5) Å), the ordered alternative (M(2) = Ru and M(3) = Rh) seems more reasonable. Similar arguments previously led to the reformulation of the disorder present in [Fe 4 CoRhC(CO) 16 ] …”

Section: Resultssupporting

confidence: 71%

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh₄]⁺Salts of the Anions [Ru₂Rh₂(CO)₇(μ-CO)₅]^2-, [Ru₂Rh₂(CO)₉(μ-CO)₃(μ-H)]^-, and [Ru₂Rh₂(CO)₇(μ-CO)₅(μ₃-AuPPh₃)]^-

Fumagalli¹,

Italia²,

Malatesta³

et al. 1996

Inorg. Chem.

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The anion [Ru 2 Rh 2 (CO) 12 ] 2-(1) has been obtained by reaction of Ru 3 (CO) 12 with [Rh(CO) 4 ] -as [N(PPh 3 ) 2 ] + or (PPh 4 ) + salts; this species reacts with acids or AuPPh 3 Cl to give respectively [Ru 2 Rh 2 (CO) 12 H] -(2) and [Ru 2 Rh 2 (CO) 12 (AuPPh 3 )] -(3). The phosphonium salts (PPh 4 ) 2 [Ru 2 Rh 2 (CO) 12 ]‚THF (I), (PPh 4 )[Ru 2 Rh 2 (CO) 12 H] (II), and (PPh 4 )[Ru 2 Rh 2 (CO) 12(AuPPh 3 )] (III) were characterized by single-crystal X-ray diffraction: I, space group P2 1 /n, Z ) 4, a ) 11.256(2) Å, b ) 26.712(2) Å, c ) 20.048(5) Å, β ) 90.45(2)°, R1 ) 0.048 for 4049 independent reflections with I > 3σ(I); II space group P2 1 /a, Z ) 4, a ) 12.453(2) Å, b ) 24.074(3) Å, c ) 13.174(2) Å, β ) 90.67(1)°, R1 ) 0.039 for 4034 independent reflections with I > 3σ(I); III, space group P2 1 /n, Z ) 4, a ) 11.720(2) Å, b ) 13.133(3) Å, c ) 35.614(2) Å, β ) 95.70( 1)°, R1 ) 0.054 for 4231 independent reflections with I > 3σ(I). Anions 1 and 2 have a tetrahedral Ru 2 Rh 2 metal frame, while in 3 there is a trigonalbipyramidal frame with one ruthenium atom and the gold atom in apical positions; in 2 the H atom bridges the Ru-Ru edge. 1 H and 31 P NMR spectra of, respectively, 2 and 3 are consistent with the crystal structures. 13 C NMR spectra of both 1 and 2 show evidence of fluxional behavior at 295 K which cannot be frozen at 178 K, where the signals collapse; compound 3 at room temperature shows a partially fluxional solution structure which becomes static at ca. 250 K.

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Section: Resultssupporting

confidence: 71%

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh₄]⁺Salts of the Anions [Ru₂Rh₂(CO)₇(μ-CO)₅]^2-, [Ru₂Rh₂(CO)₉(μ-CO)₃(μ-H)]^-, and [Ru₂Rh₂(CO)₇(μ-CO)₅(μ₃-AuPPh₃)]^-

Fumagalli¹,

Italia²,

Malatesta³

et al. 1996

Inorg. Chem.

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“…Thus, we reacted the anions [Fe 4 C(CO) 12 ] 2- and [Fe 5 C(CO) 14 ] 2- with the tricobalt cluster and were able to isolate from the reaction solutions the compounds [PPh 4 ] 2 [Fe 4 CoC(CO) 14 ] and [PPh 4 ] 2 [Fe 5 CoC(CO) 16 ], as major products resulting from condensation processes. Both of these compounds had been described earlier, and their nature was elucidated by their IR spectra and ES(−) mass spectroscopy. Consequently, the strategy shown here permits the addition of one or more cobalt fragments to the starting iron anions.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of [ClCCo₃(CO)₉] with Metal Iron Carbonyl Clusters. Formation of Carbide and Dicarbide Mixed Metal Clusters

et al. 2002

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The reaction of [ClCCo3(CO)9] with (PPh4)2[Fe3(CO)11] in CH2Cl2 at room temperature in the presence of thallium salt gives the brown cluster complex (PPh4)[Co5Fe(C2)(CO)17] (1), on which X-ray crystal structure determination has been carried out. The anion of 1 consists of two distorted Co3C and Co2FeC tetrahedra linked by a C−C bond (dicarbide unit) and by a Co−Co bond. The reactivity of [ClCCo3(CO)9] with the anions [Fe4C(CO)12]2- and [Fe5C(CO)14]2- was tested, giving [Fe4CoC(CO)14]2- and [Fe5CoC(CO)16]2-, respectively, as major products. Addition of [ClCCo3(CO)9] to a solution of [Fe3(CO)9(CCO)]2- in CH2Cl2, in the presence of thallium salt, generates the species [{Co3(CO)9}C{Fe3(CO)9(CCO)}]- (2). Subsequent addition of ethanol affords the hexametallic complex (PPh4)2[{Co3(CO)9}C{Fe3(CO)9(CCO2C2H5)}] (3), which reacts with ClAuPPh3 in a 1:3 molar ratio, in the presence of thallium salt, to form the cluster [{AuPPh3}3Fe3(CO)9(CCO2C2H5)] (4). According to its X-ray crystal determination, the anion of 4 can be described as a 48-electron Fe3 equilateral triangle capped on both sides by a μ3-CCO2C2H5 group and a AuPPh3 fragment. Additionally, two AuPPh3 units cap Fe2Au faces.

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“…In another red black Fe 4 Co cluster [30], the [(OC), 4 Fe 4^5 -C)Co]" anion represents a slightly distorted tetragonal pyramid with the Co atom in the basal plane. The M -M bond distances range from 2.538(2) to 2.649(2) A.…”

Section: Introductionmentioning

confidence: 99%

“…There are two red black Fe 4 Co clusters [29,30] for which crystallographic and structural data are available: complex [(OC) n Fe 4^5 -C)Co(CO) 3 ]~ anion [29] adopts a square -pyramidal metal framework with approximate C s symmetry. The carbide carbon is an approximately equidistant from the four basal metals and is situated 0.15 A out of the least-squares basal plane toward the side away from the apical metal.…”

Section: Introductionmentioning

confidence: 99%

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

Melnı́k¹,

Ondrejkovičová²,

Koman³

2010

Reviews in Inorganic Chemistry

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Synthesis of heteronuclear carbonyl-carbide clysters of transition metals via vertex replacement in a metal polyhedron. X-ray crystal structures of the bimetallic tetragonal-pyramidal [Fe4CoC(CO)14]− and the trimetallic octahedral Fe4CoRhC(CO)16 clusters

Cited by 23 publications

References 7 publications

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh₄]⁺Salts of the Anions [Ru₂Rh₂(CO)₇(μ-CO)₅]^2-, [Ru₂Rh₂(CO)₉(μ-CO)₃(μ-H)]^-, and [Ru₂Rh₂(CO)₇(μ-CO)₅(μ₃-AuPPh₃)]^-

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh₄]⁺Salts of the Anions [Ru₂Rh₂(CO)₇(μ-CO)₅]^2-, [Ru₂Rh₂(CO)₉(μ-CO)₃(μ-H)]^-, and [Ru₂Rh₂(CO)₇(μ-CO)₅(μ₃-AuPPh₃)]^-

Reactivity of [ClCCo₃(CO)₉] with Metal Iron Carbonyl Clusters. Formation of Carbide and Dicarbide Mixed Metal Clusters

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

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Synthesis of heteronuclear carbonyl-carbide clysters of transition metals via vertex replacement in a metal polyhedron. X-ray crystal structures of the bimetallic tetragonal-pyramidal [Fe4CoC(CO)14]− and the trimetallic octahedral Fe4CoRhC(CO)16 clusters

Cited by 23 publications

References 7 publications

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh4]+Salts of the Anions [Ru2Rh2(CO)7(μ-CO)5]2-, [Ru2Rh2(CO)9(μ-CO)3(μ-H)]-, and [Ru2Rh2(CO)7(μ-CO)5(μ3-AuPPh3)]-

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh4]+Salts of the Anions [Ru2Rh2(CO)7(μ-CO)5]2-, [Ru2Rh2(CO)9(μ-CO)3(μ-H)]-, and [Ru2Rh2(CO)7(μ-CO)5(μ3-AuPPh3)]-

Reactivity of [ClCCo3(CO)9] with Metal Iron Carbonyl Clusters. Formation of Carbide and Dicarbide Mixed Metal Clusters

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

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Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh₄]⁺Salts of the Anions [Ru₂Rh₂(CO)₇(μ-CO)₅]^2-, [Ru₂Rh₂(CO)₉(μ-CO)₃(μ-H)]^-, and [Ru₂Rh₂(CO)₇(μ-CO)₅(μ₃-AuPPh₃)]^-

Mixed Ruthenium−Rhodium Carbonyl Clusters. Synthesis and Crystal Structure of the [PPh₄]⁺Salts of the Anions [Ru₂Rh₂(CO)₇(μ-CO)₅]^2-, [Ru₂Rh₂(CO)₉(μ-CO)₃(μ-H)]^-, and [Ru₂Rh₂(CO)₇(μ-CO)₅(μ₃-AuPPh₃)]^-

Reactivity of [ClCCo₃(CO)₉] with Metal Iron Carbonyl Clusters. Formation of Carbide and Dicarbide Mixed Metal Clusters