Dimers transition metal, bonding

Transition metal—bonded carbene dimerization reactions are well-known for example, the methylene complex(57)decomposes in to give a coordinated ethylene complex [11]. 

A versatile application of Co(allyl)3 has been found in its reaction with butadiene, which effects catalytic dimerization under very mild conditions. Individual reaction steps are reproduced in Scheme 19. These reactions lead to the isolated and structurally characterized complex (13) as the true catalyst. Scheme 19 is in fact a collection of all the classical steps involved in homogeneous transition metal bond-forming reactions. The first step consists of replacement of two allyl groups by butadiene, which is reductively eliminated as diallyl, similar to what has been found with cod and with other two-or four-electron ligands. 

Particular areas of interest are the chemistry early-late metal-metal bonded complexes, main group metal-transition metal dimers, transition metal carborane derivatives, and lanthanide and actinide transition metal complexes. ... 

Transition metal carbonyl derivatives of magnesium can be prepared readily by the reductive cleavage of the metal-metal bond in numerous dimeric transition metal carbonyl complexes or by the removal of halogen from transition metal carbonyl halide complexes with an excess of 1 % magnesium amalgam in the presence of a Lewis base. These preparations may be represented by the general equations... 

Inner-Transition Metal to Transition and Inner-Transition Metal Bond 67 9.2.8. Formation of Heavy Transition Metal Group V Metal-Metal Bonds 9.2.8.3. In Discrete Niobium and Tantalum Dimeric and Trimeric Complexes... 

Molecular orbital theory explains the formation of multiple bonds both in the case of transition metal complexes as well as diatomic molecules of main group elements and compounds of these elements. There is an analogy between E2 molecules of the elements of the second period of the Periodic Chart (and their compounds containing multiple bonds) and M2 molecules as well as dimeric transition metal complexes which possess metal-metal bonds. The molecules C2, N2, and O2 have ttV , and elec-... 

Two elasses of systems illustrate eases for whieh heterolytie bond dissoeiation lies lower than the homolytie produets. The first involves transition metal dimer eations, M2. Espeeially for metals to the right side of the periodie table, sueh eations ean be eonsidered to have ground-state eleetron eonfigurations with a d d +i eharaeter, where the d eleetrons are not heavily involved in the bonding and the a bond is formed primarily from the metal atom s orbitals. If the a bond is homolytieally broken, one forms X + Y = M (s d +i)... 

Pd-cataly2ed reactions of butadiene are different from those catalyzed by other transition metal complexes. Unlike Ni(0) catalysts, neither the well known cyclodimerization nor cyclotrimerization to form COD or CDT[1,2] takes place with Pd(0) catalysts. Pd(0) complexes catalyze two important reactions of conjugated dienes[3,4]. The first type is linear dimerization. The most characteristic and useful reaction of butadiene catalyzed by Pd(0) is dimerization with incorporation of nucleophiles. The bis-rr-allylpalladium complex 3 is believed to be an intermediate of 1,3,7-octatriene (7j and telomers 5 and 6[5,6]. The complex 3 is the resonance form of 2,5-divinylpalladacyclopentane (1) and pallada-3,7-cyclononadiene (2) formed by the oxidative cyclization of butadiene. The second reaction characteristic of Pd is the co-cyclization of butadiene with C = 0 bonds of aldehydes[7-9] and CO jlO] and C = N bonds of Schiff bases[ll] and isocyanate[12] to form the six-membered heterocyclic compounds 9 with two vinyl groups. The cyclization is explained by the insertion of these unsaturated bonds into the complex 1 to generate 8 and its reductive elimination to give 9. 

Attempts have been made to catalyze the arrangement of 3-oxaquadricyclane to oxepins with transition-metal complexes.1 32 1 35 When dimethyl 2,4-dimethyl-3-oxaquadricyclane-l,5-dicarboxylate is treated with bis(benzonitrile)dichloroplatinum(II) or dicarbonylrhodium chloride dimer, an oxepin with a substitution pattern different from that following thermolysis is obtained as the main product. Instead of dimethyl 2,7-dimethyloxepin-4,5-dicarboxylate, the product of the thermal isomerization, dimethyl 2,5-dimethyloxepin-3,4-dicarboxylate (12), is formed due to the cleavage of a C O bond. This transition metal catalyzed cleavage accounts also for the formation of a 6-hydroxyfulvene [(cyclopentadienylidene)methanol] derivative (10-15%) and a substituted phenol (2-6%) as minor products.135 The proportion of reaction products is dependent on solvent, catalyst, and temperature. 

The electronic absorption and emission spectra and emission lifetimes of [Ir(/x-L)(CO)2]2 (L = pz, mpz and dmpz) have been determined.529 The intense low-energy absorption band around 400 nm is assigned to a d/2 > pz electronic transition. The three complexes all emit around 740 nm at 300 K and 670 nm at 77 K. The dimer excited states are stabilized relative to monomer levels by strong metal-metal bonding. 

The 7r-back donation stabilizes the alkene-metal 7c-bonding and therefore this is the reason why alkene complexes of the low-valent early transition metals so far isolated did not catalyze any polymerization. Some of them catalyze the oligomerization of olefins via metallocyclic mechanism [25,30,37-39]. For example, a zirconium-alkyl complex, CpZrn(CH2CH3)(7/4-butadiene)(dmpe) (dmpe = l,2-bis(dimethylphosphino)ethane) (24), catalyzed the selective dimerization of ethylene to 1-butene (Scheme I) [37, 38]. 

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