_purmal of onganomaalie Char 84 (2017 9-20, Contonts Kets evailablo at Seionesbireet Journal of Organometallic Chemistry FISFVIER journal homepage: www elsevier.com/locate/jorganchem Kinetics and mechanistic study on deoxygenation of pyridine oxide caus catalyzed by {MeReYO(pdt)} 2 dimer Abdellatif Ibdah’, Salwa Alduwikat DeparonewofCheméay Jot Univesity Science and Teds iid frdan ira iso “Te ahem alee [NEROKpaDa (where pt — 12-projsnealtiobee) catalyze he cgen aoe fected 27 Febuay 207 transfer (OAT) reaction frm the pyridine xe otphenylarsine (Phys). Therate aw is given by vk Saree Ine-aimerfeyNo} and zero erder dependence on Phys The vale of F a€ 25 °C Im CHC Ie Se aoe Wea 3 L mols The acmhaton puamecrs are AM! — 122 2 10 kal mel? and et as a8) 79.4324 cal, mo Aeconing oe popesed mecranism che rate termining sep the ‘dation of Re to ReO and he pyiane release The Wiphenyarsine enters the eaate Geter Son the rate decermring step The reason constant p~_1.4obained fom Hammett comeation vith for iy tm waste “ren: subsicatee pyridine W-cnde. The computational study inceates thatthe exidavon of FY to of to and release of he pyridine steps insenstve ro the narurecf he substituent one pyridine wath Kets the average estrated sethatenbarer ~ 115 kcal fom sie diferent sabstuted pine cides Dpopesed thar election donor substituent enrich the equlibra of the Ase stp of the proposed mechanism which isthe coordination of the pyridine oxde with one thentum atom to form ty (Scheme 2). The elecron donor substruent on the pyridine increase the concentaton fl which wil Increase ‘the rte ofthe reaction ae they ~ Ks. © 2017 Ekevier BY, all ght reserved.(CSIRO PUBLISHING “st rem ps/do.rg/ 10.107 CHIP aoe Kinetic and Computational Studies of Rhenium Catalysis for Oxygen Atom Transfer Reactions Abdellatif Ibdah,** Heba Bani Bakar,* and Salwa Alduwikat* ‘of Science and Technology, bid 22110, bdahojustedsjo The thenium(y)exo dimer {MeReO(edi)}2 (edi =1 2-ethanedihiolaie) is an effective catalyst for the oxygen atom transfer (OAT) reaction ftom pyridine oxide and picoline oxide to tiphenylarsine (Pass) as oxygen acceptor. Kinctics measurements were carticd out by the initial rate mcthod because of the monomerization reaction ofthe pyridine prodict with the (MeReO(edt)}> catalysts. The derived rate is R= k{Re][NO} (where NO is piooline oxide or pyridine oxide) and independent ofthe Ph,As concentration. The rate canstaat at room temperature in chloroform is keno) = 268.1 3.5 Lmol's~" and koyyo)= 1553 2.3 Lmol!s~. The analogue ehenium(vJoxo dimer {MeRteOpdt)}s(pat= 1.3 propanedihiclat) does not monomerize with pyridine. However, (MeReO(ed!)}» rapidly monomerizes with pyridine Density functional theory study of the enthalpy of the monomerization reaction shows that the {MeReO\edt)}. reaction with pyridine is more thermodynamically favoured than {MeReO(pdt)}» and this is attributed to the higher tangle strain on the {Me ReO (eat) bridging sulfur. The computational study ofthe propose slow step shows that enthalpy of activation (AA) of ReY oxidation to Re™ is unchanged by varying the substituent on the pyridine oxide. Manuscript received: 20 July 2017. Manuscript accepted: 30 November 2017, Published online: 19 December 2017,[| Reactivity of Rhenium Chalcogenides DOI: 10.1002/ejic.201800049 LOS oxic Full Paper I “EugiC. Thermochemistry and Bond Nature of Oxo and Thio Ligands in Rhenium(V) Catalysts and Rhenium(VIl) Intermediates: Density Functional Calculations ‘Abdellatif Ibdah**! and Salwa Alduwikat®™! Abstract: Models of cithiolate henium¥}-ox0 and -thio com: plexes and Re" (Re"0, and Re!"06) intermediates are stucied computationally using DFT(B3LYP). The analysis of the Re-E bond ( = 0, $) shows that the two lone pairs (®, ) on the ‘x0 and thio igands are strongly polarized to the fe” and fe" centers forming partial x bonds, which agree with the bond. ionder analysis of? (one 0 + two partial bonds). The lone pairs on the thio ligands are less polarized than on the oxo ligand. |e Re'0 and Re bond svengths are calculated tobe appron- Introduction Molybdenum (VAN) and tungsten(V/M) complies have been ‘widely studied, because of their central roles in oxotransferase enzyines!*! In comparison with the molybdenum (VAM) and tungsten{IV/V) systems, the ReY/Re™ system can be studhed as mately 1627 + 1.8 keal mol and 123.3 kcal mot", respec tively, The ReIO and Re"'S bond strengths are calculated to be 1187412 kealmol" and 805 £25 kcal mol”, respectwvely. The calculated oxo- and thio-thenium bond strengths and the thermochemistry of the OAT lonygen-stom transfer) cycle suo~ port that ReY¥O, and ReWOs are the key intermediates in the COAT (oxygen atom transfer) and SAT (sulfur atom transfer) reac- tions. A) Progoeed pathway for OAT reaction