Synthesis, spectral properties, and reactions of manganese and rhenium pentacarbonyl phosphine and phosphite cation derivatives and related complexes

Abstract

The synthesis of a variety of monosubstituted manganese and rhenium carbonyl cationic species of the form [M(CO)sL] [PFe] is reported, where L = group 5A ligands. Preparation of these derivatives was accomplished either through the reaction of [LM(CO)4]~w ith C2H5O2CCI followed by treatment with HBF4 (or BF3) or by thermal replacement of CH3CN in the M(CO)5(CH3CN)+ derivative. The latter procedure was shown to be the method of choice. The reaction of these pentacarbonyl derivatives with CH3NH2 to form dr-[Mn(C0)4(L)C(0)NEICH3] is discussed in relation to other nucleophilic reactions at the carbonyl carbon atom. Displacement of CO ligands from the Mn(CO)s(CH3CN)+ species in solution by pyridine, phosphines, and CH3CN is also reported. In some of these multisubstituted species, exchange of the bound CH3CN ligands was observed. The CO stretching force constants were calculated for all the cationic species prepared. In the pentacarbonylmanganese phosphine derivatives the axial CO force constant, k\, was quite similar to the equatorial CO force constant, ki. This result is discussed in terms of a direct donation of phosphorus electrons into the orbitals of the equatorial CO ligands.

Light‐ and Manganese‐Initiated Borylation of Aryl Diazonium Salts: Mechanistic Insight on the Ultrafast Time‐Scale Revealed by Time‐Resolved Spectroscopic Analysis

“…As expected, the majority of the Mnradicalr ecombined to give Mn 2 (CO) 10 as evidenced by the decrease in intensity of the negative bleach bands for the dimer. As ingle long-lived photoproduct, identified as [Mn(CO) 3 (NCMe) 3 ] + by comparison to literature data, [72] was formed (k obs = (1.88 AE 0.09) 10 5 s À1 ).…”

Reactivity of [SeFe3(CO)9]2- with Electrophiles: Formation of [SeFe2Ru3(CO)14]2-, [SeFe3(CO)9(μ-HgI)]-, Fe2(CO)6(μ-SeCHPhSe), and Se2Fe2(CO)6(μ-CH2)2

“…Further reaction of [SeFe 3 (CO) 9 ] 2- with Mn 2 (CO) 10 or [Mn(CO) 3 (MeCN) 3 ]PF 6 in MeCN, however, formed the monohydrido cluster [HSeFe 3 (CO) 9 ] - , and the methylation of [SeFe 3 (CO) 9 ] 2- also gave [HSeFe 3 (CO) 9 ] - as the major product. The tendency to form [HSeFe 3 (CO) 9 ] - in these cases is probably due to the weak affinity between these electrophiles and [SeFe 3 (CO) 9 ] 2- .…”

Syntheses and Characterization of Manganese‐Tellurolate Complexes by Using Chelating Metalloligand cis‐[Mn(Co)4(TePh)2]− and Potential Electrophilic TeMe+ Reagent

“…The bridging benzenetellurolates, terminally bonded bromine and carbonyls define the distorted octahedral geometry of Mn(2), leading to an acute angle of 84.25(4f for Te(1)-Mn(2)-Te (2). A top view of compound 1 shows the Br atom to be significantly tilted toward two tellurium atoms (Te(1)-Mn(2)-Br 81.14(4)" and 16 The oxidation process using h as the oxidant in THF produced isostructural product based on the infrared carbonyl stretching pattern and frequencies which was attributed to formation of cis-[Mn(COMIhr (reaction c in scheme II).17 Presumably, the reaction proceeded by reductive elimination followed by oxidative addition.…”