Pentacarbonyl complexes

Experimental confirmation of the metal-nitrogen coordination of thiazole complexes was recently given by Pannell et al. (472), who studied the Cr(0), Mo(0), and W(0) pentacarbonyl complexes of thiazole (Th)M(CO)5. The infrared spectra are quite similar to those of the pyridine analogs the H-NMR resonance associated with 2- and 4-protons are sharper and possess fine structure, in contrast to the broad, featureless resonances of free thiazole ligands. This is expected since removal of electron density from nitrogen upon coordination reduces the N quad-rupole coupling constant that is responsible for the line broadening of the a protons. 

The reaction of ethyl 2,2-diethoxyacrylate with alkynylalkoxycarbene complexes affords 6-ethoxy-2H-2-pyranylidene metal complexes [92] (Scheme 48). The mechanism that explains this process is initiated by a [2+2] cycloaddition reaction (see Sect. 2.3), followed by a cyclobutene ring opening to generate a tetracarbonylcarbene complex. This complex can be isolated and on standing for one day at room temperature renders the final 6-ethoxy-2Ff-pyranylidene pentacarbonyl complex. This last transformation requires the formal transfer of one carbonyl group and one proton from the diethoxy methylene moiety to the metal and to the C3 2H-pyranylidene ring, respectively, with concomitant cyclisation. Further studies on this unusual transformation have been extensively performed by Moreto et al. [93]. 

Merlic et al. were the first to predict that exposing a dienylcarbene complex 126 to photolysis would lead to an ort/zo-substituted phenolic product 129 [74a]. This photochemical benzannulation reaction, which provides products complementary to the classical para-substituted phenol as benzannulation product, can be applied to (alkoxy- and aminocarbene)pentacarbonyl complexes [74]. A mechanism proposed for this photochemical reaction is shown in Scheme 54. Photo activation promotes CO insertion resulting in the chromium ketene in-... 

Recently, the iron-promoted Barbier-type addition of alkyl halides to aromatic aldehydes has been reported (Equation (26)).326 According to the proposed mechanism, the initial step is the formation of an alkyl radical, which can be reduced to the corresponding carbanion. This carbanion nucleophile can react, while coordinated to the iron pentacarbonyl complex, with the corresponding aldehyde. This stoichiometric method is limited with respect to substrate scope and yield. The same authors have also developed the Reformatsky-type addition of cr-halosub-stituted carbonitriles to aldehydes and ketones in the presence of iron pentacarbonyl.3... 

RMn(CO)5.3 Alkylmanganese pentacarbonyl complexes are obtained by reaction of alkyl halides with NaMn(CO),. Under pressures of 2-10 kbar, these complexes undergo an insertion reaction with alkenes to give usually a single manganacycle in which the electron-withdrawing group of the alkene is attached to the same carbon atom as the metal. Demetallation is accomplished by photolysis... 

A diarsacyclobutadiene is the ligand in the tungsten pentacarbonyl complex 1 which was characterized by X-ray crystallography. 

Diethyl-1,3,2-dithiagermolane (336) reacts with the chromium pentacarbonyl complex of dichlorogermylene (in the form of solvate with THF) to give a cyclic germylene complex (337) which can be further stabilized with an additional nitrone ligand <87JOM(33i)ii>. 

It is, however, for the transition metals themselves that DFT has proven to be a tremendous improvement over HF and post-HF methods, particularly for cases where tlie metal atom is coordinatively unsaturated. The narrow separation between filled and empty d-block orbitals typically leads to enormous non-dynamical correlation problems with an HF treatment, and DFT is much less prone to analogous problems. Even in cases of a saturated coordination sphere, DFT methods typically significantly ouqierform HF or MP2. Jonas and Thiel (1995) used the BP86 functional to compute geometries for the neutral hexacarbonyl complexes of Cr, Mo, and W, the pentacarbonyl complexes of Fe, Ru, and Os, and the tetracarbonyl... 

Simple alkenes, norbomene and styrene do not undergo cyclopropanation or insertion reactions with cyclopropyl(methoxy)carbene chromium pentacarbonyl complex. However, the conjugated 1-vinylcyclopentene is cyclopropanated under the reaction conditions at the terminal double bond, affording an isomeric mixture (trans cis = 40 60), in 66% yield (equation 72). 

D. Paramagnetic Mono- and Dinuclear Pentacarbonyl Complexes of Chromium... 

We have thus been able to show that the acetonitrile-pentacarbonyl complexes M(CO)5NCMe (M = Cr, Mo, W) and cycloheptatriene-iron-tricarbonyl C7H3Fe(CO)3 are deprotonated as follows, without attack at the CO ligands (151). 

OM802>. In some cases the tungsten pentacarbonyl complexes 52 and 53 were prepared as more stable products, to aid characterization. Key NMR data are presented. 

The facile decarbonylation of pentacarbonyl complexes 23a and 23b results in tetra-carbonyl carbene complex intermediates 24a and 24b, respectively. Their annulation can produce benzene and/or cyclopentadiene derivatives 25 and/or 26. In the case of aryl acyla-mino complex 23a, the reaction course is shifted towards the benzannulation reaction (25a 26a = 84 16). With the vinyl carbene complex 23b, the benzannulation product 25b (25b 26b = 100 0) is produced exclusively. 

The novel cobalt complex came about as a result of the intramolecular coordination of a double bond, present in one of the R groups on the acetylene, to one of the cobalt atoms - taking the place of a CO ligand (67 - 68). They found that the new pentacarbonyl complex could be readily formed in CDC13 at room temperature from the hexacarbonyl dicobalt precursor. Attempts to use the pentacarbonyl complex as a substrate in the PK reaction led to no formation of cyclopentenone product. It was proposed that this is due to the alkene occupying a pseudo-equatorial site -alkene insertion is thought to occur from the axial position (see section 2.4). 

The expected hexacarbonyl dicobalt complex was formed when the al-kyne and dicobalt octacarbonyl were stirred in CH2C12 (73 —> 74). If the same reaction was performed in the presence of ten equivalents of NMO, the novel pentacarbonyl complex could be isolated (73->75). On dissociation of the CO ligand, accelerated by the addition of NMO, the sulfur atom is able to coordinate to the vacant site creating a stable complex. Treatment of the complex with CO resulted in regeneration of the hexacarbonyl complex and, unlike the isolated alkene-pentacarbonyldicobalt-alkyne species 68, heating of the pentacarbonyl complex 75 led to the formation of the desired cyclopentenone. A similar sulfur stabilised intermediate was isolated by Pericas and co-workers while investigating tethered chiral auxiliaries in the PK reaction.87,88... 

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