Organische Mangan‐Verbindungen

High-valent Organomanganese Compounds

“…Above 230 K , the compounds display magnetic moments o f ca. 6.0 |i B per Mn" center that are only slightly above the spin-only value for five unpaired electrons. Several of these complexes have also been characterized by x-ray crystallography.…”

“…The x-ray crystal structure o f low-spin (r|-Cp*) 2 Mn has been determined at three different temperatures in order to provide additional insights into the molecular distortions seen in earlier studies. 73 " 6 The Cp* rings in this complex are staggered and slightly slipped.…”

“…94 The reaction of manganocene with V(CO) 6 affords the manganese(I) tricarbonyl (r|-Cp)Mn(CO) 3 . 96 IR studies of the reactions of CO with Cp 2 Mn adsorbed onto A 1 P O 4 and SiO 2 % and in frozen solution 98 have been reported.…”

“…24 ' 25 The He 1 and H e 1 1 photoelectron spectra and variable-temperature magnetic susceptibility have been reported for Mn[CH(TMS) 2 ] 2 ; a SCF MO calculation on the hypothetical monomer MnMe 2 has also been carried out. 21 \ M n / C Ph 2 P -2^ PPh 2 c c (6) Organic isocyanates insert into the manganese-alkyl bonds of the neopentyl and neophyl complexes [Mn(CH 2 Bu t ) 2 ] 4 and [Mn(CH 2 CMe 2 Ph) 2 ] 2 ; the products form colorless crystals and are the first organomanganese intermediates to be isolated f r o m the reaction of an organomanganese(II) reagent with an organic substrate. 5 Hydrolysis of the products gives the corresponding organic amide R 1 C(O)NHR 2 5 Manganese(II) dialkyls react with the weak acids 2,4,6-tri(Bu t )phenol and di(Bu ^phosphine to yield one equivalent o f alkane per metal center and the organomanganese(II) species Mn 2 (CH 2 CMe 2 Ph) 2 -(^i-OC 6 H 2 Bu t 3 ) 2 (7) and Mn 2 (CH 2 CMe 3 ) 2 ()i-PBu t 2 ) 2 (8), respectively (Scheme I).…”

“…5 was claimed to be a single pure species, it was not considered whether this material could be a 1 : 1 mixture of the mono-and diadducts. With excess ^-butylisonitrile, MnI 2 (PPh 3 ) 2 reacts in toluene to give two complexes, one o f which is the [Mn(CNBu l ) 6 ] + salt of the [MnI 3 (CNBu ! )]~ anion.…”