A New Metal Carbonyl Synthesis<sup>1</sup>

Closson, Rex D.; Buzbee, Lloyd R.; Ecke, George G.

doi:10.1021/ja01556a005

Cited by 36 publications

(14 citation statements)

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“…The homoleptic Mn 2 (CO) 10 was discovered relatively recently compared with many of the other simple homoleptic carbonyls of the first row transition metals and requires somewhat unusual methods for its synthesis by reductive carbonylation of suitable manganese compounds under carbon monoxide pressure. [6][7][8] However, Mn 2 (CO) 10 is the most stable of the homoleptic binuclear carbonyls of the first row transition metals and can even be purified by steam distillation without significant decomposition. The binuclear chromium carbonyl nitrosyl Cr 2 (NO) 2 (CO) 8 can be obtained by oxidation of the Cr(NO)(CO) 4 À anion.…”

Section: Introductionmentioning

confidence: 99%

Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Chang

Xie

et al. 2012

New J. Chem.

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Section: Introductionmentioning

confidence: 99%

Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Chang

Xie

et al. 2012

New J. Chem.

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“…The first manganese carbonyl, Mn 2 (CO) 10 , was obtained initially in 1954 in trace quantities by an unreliable synthesis. 2 The first reliable method of synthesizing Mn 2 (CO) 10 in quantity was developed only in 1958, 3 more than a quarter of a century after the original discovery of H 2 Fe(CO) 4 and HCo(CO) 4 . Almost immediately after Mn 2 (CO) 10 thus became available, Hieber and Wagner 4 used it to synthesize HMn(CO) 5 for the first time.…”

Section: Introductionmentioning

confidence: 99%

Mononuclear and binuclear manganese carbonyl hydrides: the preference for bridging hydrogens over bridging carbonyls

Liu

Wang

et al. 2009

Dalton Trans.

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The structures of the mononuclear derivatives HMn(CO)n (n=4 and 3) are shown by density functional theory (B3LYP and PB86) to derive from octahedral HMn(CO)5 by losses of various combinations of carbonyl groups with relatively little change in the C-Mn-C angles involving the remaining carbonyl groups. The binuclear H2Mn2(CO)n structures are predicted to have bridging hydrogen atoms in preference to bridging carbonyl groups. Thus, two structures are found for the binuclear H2Mn2(CO)9, isoelectronic with Fe2(CO)9, in which all nine of the carbonyl groups are terminal carbonyl groups. The lowest lying H2Mn2(CO)9 structure is the dihydrogen complex (OC)5Mn-Mn(CO)4(eta2-H2), in which one of the equatorial CO groups of Mn2(CO)10 is replaced by a dihydrogen ligand. A slightly higher energy H2Mn2(CO)9 structure by approximately 6 kcal mol(-1) has an Mn-Mn bond bridged by a single hydrogen and all terminal carbonyl groups as well as a single terminal hydrogen. The H2Mn2(CO)8 molecule is predicted to have a structure with a central Mn(micro-H)2Mn core related to diborane. In this structure the manganese-manganese bond of length 2.703 A (BP86) can be considered the diprotonated formal double bond required to give both manganese atoms the favoured 18-electron configuration. The more highly unsaturated H2Mn2(CO)n (n=7, 6) derivatives have similar structures derived from the H2Mn2(CO)8 structure by loss of one or two carbonyl groups. In many cases the Mn[triple bond, length as m-dash]Mn distance in the central Mn(micro-H)2Mn unit shortens to approximately 2.4 A suggesting a diprotonated triple bond.

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“…However, development of the chemistry of (alkyne)Mn 2 (CO) 8 derivatives has been much more limited than that of the chemistry of (alkyne)Co 2 (CO) 6 derivatives. This relates to limited availability of the Mn 2 (CO) 10 starting material in quantity before 1958, [12,13] as well as its much lower reactivity towards alkynes. The first examples of (alkyne)Mn 2 (CO) 8 derivatives were the aminoalkyne derivatives (Et 2 NC 2 NEt 2 )Mn 2 (CO) 8 , (Et 2 NC 2 Me)Mn 2 (CO) 8 , and (Me 2 NC 2 Ph)Mn 2 (CO) 8 synthesized by King and Harmon in 1976 [14] by photolysis of the alkyne with Mn 2 (CO) 10 as part of a general study of reactions of aminoalkynes with metal carbonyls.…”

Section: Introductionmentioning

confidence: 99%

Binuclear Alkyne Manganese Carbonyls: Their Rearrangements to Allene, Allyl, and Vinylcarbene Derivatives by Hydrogen Migration from Methyl Substituents

Wang

et al. 2021

Eur J Inorg Chem

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Binuclear alkyne manganese carbonyls of the type (RC≡CR')Mn2(CO)n (R and R'=methyl or dimethylamino; n=8, 7, 6) and their isomers related to the experimentally known (MeC2NEt2)Mn2(CO)n (n=8, 7) structures have been investigated by density functional theory. The alkyne ligand remains intact in the only low energy (Me2N)2C2Mn2(CO)8 isomer, which has a central Mn2C2 tetrahedrane unit and is otherwise analogous to the well‐known (alkyne)Co2(CO)6 derivatives except for one more CO group per metal atom. The low‐energy structures of the unsaturated (Me2N)2C2Mn2(CO)n (n=7, 6) systems include isomers in which the nitrogen atom of one of the dimethylamino groups as well as the C≡C triple bond of the alkyne is coordinated to the central Mn2 unit. In other low‐energy (Me2N)2C2Mn2(CO)n (n=7, 6) isomers the alkyne C≡C triple bond has broken completely to form two separate bridging dimethylaminocarbyne Me2NC ligands analogous to the experimentally known iron carbonyl complex (Et2NC)2Fe2(CO)6. The (alkyne)Mn2(CO)n (n=8, 7, 6) systems of the alkynes MeC≡CMe and Me2NC≡CMe with methyl substituents have significantly more complicated potential surfaces. In these systems the lowest energy isomers have bridging ligands derived from the alkyne in which one or two hydrogen atoms have migrated from a methyl group to one or both of the alkyne carbon atoms. These bridging ligands include allene, manganallyl, and vinylcarbene ligands, the first two of which have been realized experimentally in research by Adams and coworkers. Theoretical studies suggest that the mechanism for the conversion of the simple alkyne octacarbonyl (MeC2NMe2)Mn2(CO)8 to the dimethylaminomanganaallyl complex Mn2(CO)7[μ‐η4‐C3H3Me2] involves decarbonylation to the heptacarbonyl and the hexacarbonyl complexes. Subsequent hydrogen migrations then occur through intermediates with C−H−Mn agostic interactions to give the final product. Eight transition states for this mechanistic sequence have been identified with activation energies of ∼20 kcal/mol for the first hydrogen migration and ∼14 kcal/mol for the second hydrogen migration.

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A New Metal Carbonyl Synthesis¹

Cited by 36 publications

References 1 publication

Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Mononuclear and binuclear manganese carbonyl hydrides: the preference for bridging hydrogens over bridging carbonyls

Binuclear Alkyne Manganese Carbonyls: Their Rearrangements to Allene, Allyl, and Vinylcarbene Derivatives by Hydrogen Migration from Methyl Substituents

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A New Metal Carbonyl Synthesis1

Cited by 36 publications

References 1 publication

Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Binuclear iron boronyl carbonyls isoelectronic with the well-known decacarbonyldimanganese

Mononuclear and binuclear manganese carbonyl hydrides: the preference for bridging hydrogens over bridging carbonyls

Binuclear Alkyne Manganese Carbonyls: Their Rearrangements to Allene, Allyl, and Vinylcarbene Derivatives by Hydrogen Migration from Methyl Substituents

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A New Metal Carbonyl Synthesis¹