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Molecular and supported Ti(iii)-alkyls: efficient ethylene polymerization driven by the π-character of metal-carbon bonds and back donation from a singly occupied molecular orbital.

ABSTRACT: While Ti(iii) alkyl species are the proposed active sites in Ziegler-Natta ethylene polymerization catalysts, the corresponding well-defined homogeneous catalysts are not known. We report that well-defined neutral β-diiminato Ti(iii) alkyl species, namely [Ti(nacnac)(CH₂ ^t Bu)₂] and its alumina-grafted derivative [(Al_sO)Ti(nacnac)(CH₂ ^t Bu)], are active towards ethylene polymerization at moderate pressures and temperatures and possess an electron configuration well-adapted to insertion of ethylene. Advanced EPR spectroscopy showed that ethylene insertion into a Ti(iii)-C bond takes place during polymerization from Ti(nacnac)(CH₂ ^t Bu)₂. A combination of pulsed EPR spectroscopy and DFT calculations, based on a crystal structure of [Ti(nacnac)(CH₂ ^t Bu)₂], enabled us to reveal details about the structure and electronic configurations of both molecular and surface-grafted species. For both compounds, the α-agostic C-H interaction, which involves the singly occupied molecular orbital, indicates a π character of the metal-carbon bond; this π character is enhanced upon ethylene coordination, leading to a nearly barrier-less C₂H₄ insertion into Ti(iii)-C bonds after this first step. During coordination, back donation from the SOMO to the π*(C₂H₄) occurs, leading to stabilization of π-ethylene complexes and to a significant lowering of the overall energy of the C₂H₄ insertion transition state. In d¹ alkyl complexes, ethylene insertion follows an original "augmented" Cossee-Arlman mechanism that involves the delocalization of unpaired electrons between the SOMO, π*(C₂H₄) and σ*(Ti-C) in the transition state, which further favors ethylene insertion. All these factors facilitate ethylene polymerization on Ti(iii) neutral alkyl species and make d¹ alkyl complexes potentially more effective polymerization catalysts than their d⁰ analogues.

SUBMITTER: Ashuiev A

PROVIDER: S-EPMC8178971 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:For soybean, novel single dominant Resistance to Phytophthora sojae (Rps) genes are sought to manage Phytophthora root and stem rot. In this study, resistance to P. sojae was mapped individually in four recombinant inbred line (RIL) populations derived from crosses of the susceptible cultivar Williams with PI 407985, PI 408029, PI 408097, and PI424477 previously identified as putative novel sources of disease resistance. Each population was screened for resistance with five to seven isolates of P. sojae separately over multiple F7-F10 generations. Additionally, three of the populations were screened with inoculum from the combination of three P. sojae isolates (PPR), which comprised virulence to 14 Rps genes. Over 2,300 single-nucleotide polymorphism markers were used to construct genetic maps in each population to identify chromosomal regions associated with resistance to P. sojae. Resistance segregated as one or two genes to the individual isolates and one gene toward PPR in each population and mapped to chromosomes 3, 13, or 18 in one or more of the four RIL populations. Resistance to five isolates mapped to the same chromosome 3 region are as follows: OH7 (PI 424477 and PI408029), OH12168, OH7/8, PPR (PI 407985), and 1.S.1.1 (PI408029). The resistance regions on chromosome 13 also overlapped for OH1, OH25, OH-MIA (PI424477), PPR (PI 424477, PI 407985, and PI 408097), PPR and OH0217 (PI 408097), and OH4 (PI 408029), but were distinct for each population suggesting multiple genes confer resistance. Two regions were identified on chromosome 18 but all appear to map to known loci; notably, resistance to the combined inoculum (PPR) did not map at this locus. However, there are putative new alleles in three of four populations, three on chromosome 3 and two on chromosome 13 based on mapping location but also known virulence in the isolate used. This characterization of all the Rps genes segregating in these populations to these isolates will be informative for breeding, but the combined inoculum was able to map a novel loci. Furthermore, within each of these P. sojae isolates, there was virulence to more than the described Rps genes, and the effectiveness of the novel genes requires testing in larger populations.

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Molecular and supported Ti(iii)-alkyls: efficient ethylene polymerization driven by the π-character of metal-carbon bonds and back donation from a singly occupied molecular orbital.

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