Carbonylation of the ruthenium-methyl bond of Ru(Me)(I)(CO)2(i-Pr-N:CHCH:N-i-Pr) catalyzed by Ru(CO)4(PR3), ZnCl2, and H+

Five-Coordinate Complex [RuHCl(CO)(PPri3)2] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η1-Carbon Ligands

“…The most interesting features of the structure are those related to the α,β-unsaturated acyl ligand. The Ru−C(1) bond length of 2.060(2) Å is similar to those found in the complexes [PPN][Ru 6 C(CO) 16 {C(O)Me}] (2.099(12) Å) and [Ru{C(O)Me}I(CO) 2 (Pr i -DAB)] (2.078(8) Å) and about 0.1 Å longer than that found in the five-coordinate derivative [Ru{C(O)Me}Cl(CO)(PPr i 3 ) 2 ] (1.957(6) Å) . The Ru−C(1)−O(1) and Ru−C(1)−C(2) angles are 123.9(2) and 116.1(2)°, and the C(1)−O(1) bond length is 1.212(3) Å, as expected for a CO double bond of an η 1 -acyl ligand.…”

Ruthenium‐Catalyzed Dehydrogenation Through an Intermolecular Hydrogen Atom Transfer Mechanism

“…Instead, the addition of mesityl iodide to pre‐formed complex I or II led to a full conversion to a new complex. In contrast to what has been reported with other classes of diimine ligands bearing alkyl substituents on the backbone instead of aryl groups, it was not possible to observe or isolate any of the oxidative addition products [37] . Instead, the trans carbonyl insertion complex III was obtained (Figure 1 b, bottom) along with the diiodo ruthenium complex IV .…”

“…In contrast to what has been reported with other classes of diimine ligands bearing alkyl substituents on the backbone instead of aryl groups,itwas not possible to observe or isolate any of the oxidative addition products. [37] Instead, the trans carbonyl insertion complex III was obtained (Figure 1b,b ottom) along with the diiodo ruthenium complex IV.I nc ontrast to complex I,t hese two complexes both exhibit an octahedral geometry,w ith RuÀN and C À Nb ond lengths and angles within the range of aR u II complex with dative nitrogen coordination, indicating amore classical behavior of the neutral diimine ligand in this oxidized state.W et hen set out to evaluate the catalytic and kinetic competence of all the isolated ruthenium complexes for the dehydrogenation of cyclooctane.C omplexes III and IV only gave trace amounts of the product (Supporting Information, Table S4), suggesting that these species are possible deactivation products.More importantly,the di-iodo species IV could be observed by 19 FNMR spectroscopy under catalytic conditions and its concentration steadily increased over the course of the reaction (Supporting Information, Figure S4). This observation, when combined with the catalytic incompetence observed above,c learly suggests that the formation of the di-iodo species is the major deactivation pathway under the reaction conditions.T his result provides critical information for the design of second-generation catalysts for this transformation.…”

Synthesis, structure and spectroscopic properties of novel metal-metal bonded manganese-ruthenium complexes with α-diimine ligands. X-ray structure of [(CO)5MnRu(Me)(CO)2(σ(N′)-iPr-PyCa)] (iPr-PyCa = pyridine-2-carbaldehyde-N-isopropylimine)

“…These distances are somewhat larger than found for [Ru(I)(C(O)Me)(CO)z(iPr-DAB)] (2.0788(8) /~) [26] and [Ru(CF3SO3)(Me)(CO)2(iPr-DAB)] (2.122(10) /~) [26] due to the larger trans effects of the Mn(CO)5 and Me groups with respect to I-and CF3SO 3-. The Ru-CO bonds ( ~ 1.863(5)/~) are slightly longer than in these mononuclear complexes (1.840(9) /k), but comparable with the 1.867(5) z~ Ru-CO bonds in [Ru(Me)(CO)2(iPr-DAB)]2 [24].…”