Oxidative-addition of the N–H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os3(CO)10(μ-H)(μ-sac)

Activation of thiosaccharin at a polynuclear osmium cluster

“…While numerous studies on the reactivity of sacH with metal compounds are known, to our knowledge, only two reports appear in the literature on the reaction of saccharin with low-valent metal clusters [18,19]. In 2006, Buck and Maas reported the isolation of the di-and tetra-ruthenium complexes, [Ru2(CO)6(μ-sac)2] and [Ru4(CO)12(μ-sac)4], respectively, from the reactions of Ru3(CO)12 with excess sacH at elevated temperatures [18].…”

“…Recently, we reported the first triosmium clusters containing an ancillary sac ligand from the reactions of [Os3(CO)10-n(NCMe)n] (n = 1, 2) with sacH in refluxing benzene. Scheme 1 illustrates the reaction that gives [HOs3(CO)10(μ-N,O-1,2-sac)], whose reactivity with monodentate phosphines, PR3 (R = Ph, Th, Fu) was examined in our report and found to afford the corresponding mono-and bis-phosphine substituted derivatives [HOs3(CO)9(PR3)(μ-N,O-1,2-sac)] and [HOs3(CO)8(PR3)2(μ-N,O-1,2-sac)], respectively [19]. The coordinated sac ligand maintains a μ-N,O coordination mode in the products and is believed to play a pivotal role as a spectator ligand that helps to direct the phosphine regiochemistry associated with these substitution reactions.…”

“…The asymmetric unit of 2 also contains two independent molecules that do not show any significant structural differences, allowing us to limit our discussion to the structure that is depicted 1) 117.7(4o ] provide space for the hydride to bridge the Os(1)-Os(2) edge in a manner similar to the hydride ligand in the corresponding saccharinate analog [HOs3(CO)10(μ-N,O-1,2-sac)] [19]. The location of the hydride at the heterocyclic bridged Os-Os bond receives additional support from the comprehensive report recently published by us where the energies of hydride isomers at related heterocyclic-bridged triosmium clusters were examined by DFT [38].…”

Bis{3-(2-amino-benzilimino)-pentan-2-on oksimato}kobalt(III) sakkarinat monohidrat kompleksinin sentezi, karakterizasyonu ve teermal özellikleri

“…Sakkarin ve deprotonasyonu sonucu oluşan sakkarinat anyonu metal iyonlarına değişik uçlardan (bir imin azotu, bir karbonil oksijeni, iki sülfonil oksijeni) bağlanabilmektedir [28,29]. Sakkarinin biyolojik önemi nedeniyle sakkarinat içeren metal komplekslerine ilgi çok fazladır.…”

“…Sakkarinin biyolojik önemi nedeniyle sakkarinat içeren metal komplekslerine ilgi çok fazladır. Sakkarinat iyonu koordinasyon bileşiklerinde tamamlayıcı iyon [30][31][32][33][34][35] veya koordine ligand [28,29,[31][32][33]36] olabildiği gibi bazı bileşiklerde hem ligand hem de tamamlayıcı iyon olarak bulunabilmektedir [34,[37][38][39]. Son yıllarda özellikle N-verici ligandlar ve sakkarinat içeren metal komplekslerinin çalışmalarına rastlanmaktadır [30][31][32][33][34][35][36][37][38][39].…”