Notes- Reductive Carbonylation Synthesis of Metal Carbonyls. V. Synthesis of Manganese Carbonyl from π-Methylcyclopentadienylmanganese Tricarbonyl

Podall, H. E.; Giraitis, Albert P.

doi:10.1021/jo01351a637

Cited by 17 publications

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“…In retrospect, loss of the cyclopentadienyl group from CpMn(CO) 3 might have been anticipated from its reaction with Na in HMPA. Thus, Podall and Giraitis had previously shown that treatment of the methylcyclopentadienyl analogue, MeCpMn(CO) 3 , with Na metal in hot (125 °C) diglyme [bis(2-methoxyethyl) ether] under about 50 atm of pressure of CO, followed by hydrolysis and steam distillation, afforded about a 50% yield of Mn 2 (CO) 10 . They proposed that the first step in the reaction involved a reductive cleavage of the methylcyclopentadienylmanganese unit, as depicted by eq 12 …”

Section: Metal Carbonyl Mono- and Dianionsmentioning

confidence: 99%

“…Thus, Podall and Giraitis had previously shown that treatment of the methylcyclopentadienyl analogue, MeCpMn(CO) 3 , with Na metal in hot (125 °C) diglyme [bis(2-methoxyethyl) ether] under about 50 atm of pressure of CO, followed by hydrolysis and steam distillation, afforded about a 50% yield of Mn 2 (CO) 10 . They proposed that the first step in the reaction involved a reductive cleavage of the methylcyclopentadienylmanganese unit, as depicted by eq 12 Although ferrocene was earlier shown to be completely reduced by Li metal in ethylamine or liquid ammonia to Fe metal and LiCp, Podall's reduction seems to be the first reaction of this type to afford a reduced transition-metal complex.…”

Section: Metal Carbonyl Mono- and Dianionsmentioning

confidence: 99%

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Adventures with Substances Containing Metals in Negative Oxidation States

2006

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A brief history of substances containing s,p- and d-block metals in negative oxidation states is described. A classification of these species and discussions of formal oxidation state assignments for low-valent transition metals in complexes are included, along with comments on the innocent and noninnocent character of ligands in metalates. Syntheses of highly reduced carbonyl complexes formally containing transition metals in their lowest known oxidation states of III- and IV- are discussed. Atmospheric-pressure syntheses of early-transition-metal carbonyls involving alkali-metal polyarene-mediated reductions of non-carbonyl precursors have been developed. In the absence of carbon monoxide, these reactions afford homoleptic polyarenemetalates, including the initial species containing three aromatic hydrocarbons bound to one metal. In several instances, these metalates function as useful synthons for "naked" spin-paired atomic anions of transition metals.

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Section: Metal Carbonyl Mono- and Dianionsmentioning

confidence: 99%

Section: Metal Carbonyl Mono- and Dianionsmentioning

confidence: 99%

Adventures with Substances Containing Metals in Negative Oxidation States

2006

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“…These corresponding dihedral angles of the cluster agree with Dih symmetry of the metal-halogen skeleton of the three clusters. The dihedral angles In-Mn-Cax In-Mn01-C01 In-Mn01-C03 In-Mn01-C04 In-Mn02-C07 In-Mn02-C08 In-Mn02-C09 In-Mn02-C10 002-007 or 002'-007 ' 3.155 (10) 3.173 (9) 3.189 (12) 005-007 or 005 -007' 3.237 (10) 3.278 (10) 3.331 (12) of each cluster between the Mn01-Mn02-Mn01,-Mn02/ plane and the plane with axial C atoms CO 1-C06-C01 '-C06' (X = Cl, 0.42°; X = Br, 0.25°; X = I, 0.18°) as well as with the 3.082 (9) 3.135 (10) 008-009'or 008 -009 3.097 (10) 3.073 (9) 3.067 (11) 002-010'or002'-010 3.028 (9) 3.030(9) 3.068 (11) 010-010' 3.041 (10) 3.062(9) 3.142 (10) plane with the atoms OOl-006-001'-006' (X = Cl, 0.29°; X -Br, 0.44°; X = I, 0.77°) show that these atoms are fairly close to being in one plane.…”

Section: Discussionmentioning

confidence: 99%

Single-crystal x-ray analysis of compounds with a covalent metal-metal bond. 5. Characterization of halogeno-bridged structures of three dimers of halogenobis(pentacarbonylmanganio)indium(III), [(Mn(CO)5)2In(.mu.-X)]2 (X = chlorine, bromine, iodine)

Haupt¹,

Wolfes²,

Preut³

1976

Inorg. Chem.

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The oxidative insertion of In'X into the Mn-Mn bond of Mn2(CO)io in the presence of xylene led to clusters of the type [(Mn(CO)s)2ln(M-X)]2 (X = Cl, Br, I). All three clusters were characterized by osmometric, thermogravimetric, mass spectroscopic, ir, and Raman spectroscopic measurements. X-ray structural analysis shows that the three clusters are isomorphous and have similar molecular structures. The central molecular fragment of each cluster contains a planar centrosymmetric four-membered In2X2 ring. Each In atom is bonded to two µatoms and to two Mn atoms in a distorted tetrahedral arrangement. The plane defined by the four Mn atoms is perpendicular to that defined by the 1^X2 atoms. The Mn-In-Mn angles of the three clusters have the following values: X = Cl, 123.59 (3)0; X = Br, 124.97 (3)°; X = I, 126.37 (4)°. The shortest intramolecular nonbonding O-O contact lengths correspond to equatorial CO ligands of the two pairs of Mn(CO)s ligands above or below the In2X2 plane (X = Cl, 2.877 (8) Á; X = Br, 2.896 (8) Á; X = I, 2.963 (9) A) and signify a dependence of the 0-0 repulsion interaction on the atomic size of the µatoms. A consequence of the repulsive effect connected with the nonbonded interaction of the equatorial CO groups of the different Mn atoms is their staggered arrangement. The In2X2 rings have obtuse -(µ-)-(X = Cl, 100.02 (5)°; X = Br, 97.42 (2)°; X = I, 94.35 (2)°) and acute (µ-)--(µ-) angles (X = Cl, 79.98 (5)°; X = Br, 82.58 (2)°; X = I, 85.65 (2)°) and the order of the nonbonded lengths In-In and X-X is In-In > X-X. These structural features of the 1^X2 rings are reversed with respect to corresponding features of the In2U ring of the compound [ 2 (µ-)]2 (acute -(µ-)angle, obtuse (µ-)--(µ-) angle, and the order of the length In-In < X-X), in which no comparable repulsion exists between the terminal ligands. The average In-X distances in the clusters examined are for X = Cl, 2.618 (2) Á, for X = Br, 2.757

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Darstellung von Ga₂[Mn(CO)₅]₄ und In[Mn(CO)₅]₃

Haupt

Neumann

1972

Zeitschrift anorg allge chemie

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Bei der Umsetzung von metallischem Gallium mit Mn2(CO)10 im Bombenrohr wurden rote Kristalle der formalen Zusammensetzung Ga2[Mn(CO)5]4 erhalten. IR‐ und Raman‐Spektrum dieser Verbindung lassen auf das Vorhandensein sowohl von Ga–Mn‐Bindungen als auch Ga–Ga‐Bindungen und auf das Vorliegen eines für Metalle der III. Hauptgruppe bisher unbekannten Metallgerüstes Mn–Ga–Ga(Mn)3 schließen. Nach der gleichen neuartigen Darstellungsmethode, jedoch unter Zusatz von Xylol, wurde In[Mn(CO)5]3, welches eine InMn3−Verknüpfung von D3h‐Symmetrie hat, gewonnen.

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Notes- Reductive Carbonylation Synthesis of Metal Carbonyls. V. Synthesis of Manganese Carbonyl from π-Methylcyclopentadienylmanganese Tricarbonyl

Cited by 17 publications

References 0 publications

Adventures with Substances Containing Metals in Negative Oxidation States

Adventures with Substances Containing Metals in Negative Oxidation States

Single-crystal x-ray analysis of compounds with a covalent metal-metal bond. 5. Characterization of halogeno-bridged structures of three dimers of halogenobis(pentacarbonylmanganio)indium(III), [(Mn(CO)5)2In(.mu.-X)]2 (X = chlorine, bromine, iodine)

Darstellung von Ga₂[Mn(CO)₅]₄ und In[Mn(CO)₅]₃

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Notes- Reductive Carbonylation Synthesis of Metal Carbonyls. V. Synthesis of Manganese Carbonyl from π-Methylcyclopentadienylmanganese Tricarbonyl

Cited by 17 publications

References 0 publications

Adventures with Substances Containing Metals in Negative Oxidation States

Adventures with Substances Containing Metals in Negative Oxidation States

Single-crystal x-ray analysis of compounds with a covalent metal-metal bond. 5. Characterization of halogeno-bridged structures of three dimers of halogenobis(pentacarbonylmanganio)indium(III), [(Mn(CO)5)2In(.mu.-X)]2 (X = chlorine, bromine, iodine)

Darstellung von Ga2[Mn(CO)5]4 und In[Mn(CO)5]3

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Darstellung von Ga₂[Mn(CO)₅]₄ und In[Mn(CO)₅]₃