Soluble Yttrium Chalcogenides:  Syntheses, Structures, and NMR Properties of Y[η³-N(SPPh₂)₂]₃ and Y[η²-N(SePPh₂)₂]₂[η³-N(SePPh₂)₂]

Abstract

The compounds Y[N(QPPh2)2]3 (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe3)2]3 and HN(QPPh2)2 in methylene chloride (CH2Cl2). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh2)2]- ligands bound eta 3 through two S atoms and an N atom. The molecule possesses D3 symmetry, as determined in the solid state by X-ray crystallography and in solution by 89Y and 31P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh2)2]- ligands, but two are bound eta 2 through the two Se atoms and the other ligand is bound eta 3 through the two Se atoms and an N atom. Although a fluxional process is detected in the 31P and 77Se NMR spectra, a triplet is found in the 89Y NMR spectrum of 2 (delta = 436 ppm relative to YCl3 in D2O, 2JY-P = 5 Hz). This implies that on average the conformation of one eta 3- and two eta 2-bound ligands is retained in solution. Crystallographic data for 1: C72H60N3P6S6Y, rhombohedral, R3c, a = 14.927(5) A, c = 56.047(13) A, V = 10815(6) A3, T = 153 K, Z = 6, and R1(F) = 0.042 for the 1451 reflections with I > 2 sigma(I). Crystallographic data for 2: C72H60N3P6Se6Y.Ch2-Cl2, monoclinic, P2(1)n, a = 13.3511(17) A, b = 38.539(7) A, c = 14.108(2) A, beta = 94.085(13) degrees, V = 7241(2) A 3, T = 153 K, Z = 4, and R1(F) = 0.037 for the 8868 reflections with I > 2 sigma(I).

Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen–Chalcogen Bonded Dimers and a Novel Selone

“…In contrast to the extensively studied N-bridged, monoanionic ligands [NA C H T U N G T R E N N U N G (PPh 2 E) 2 ] À (1, E= S, Se), which predominantly form E,E-chelated metal complexes without the participation of the N atom, [1,2] the isoelectronic C-bridged dianion [CA C H T U N G T R E N N U N G (PPh 2 S) 2 ] 2À (2) exhibits strong metal-carbon interactions in a variety of coordination complexes. The first example, a binuclear Pt II complex of 2, involved bis-C,S-chelation and a quaternary carbon bridging the two metal centres.…”

“…Unusual carbon-centred reactivity is also observed in the redox behaviour of compounds 2. In contrast with the formation of chalcogen-chalcogen bonds upon oxidation of Nbridged ligands of type 1, [11] treatment of Li 2 2 with the mild oxidising agents C 2 Cl 6 or I 2 produces remarkably stable monomeric or dimeric carbenoids, respectively. [12,13] The nu- Keywords: chalcogens · electronic structure · oxidation · radicals · tridentate ligands…”

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

“…[13] The diselenoimido-diphosphinato ligand can also stabilize a wide range of metal coordination spheres including alkali metals, [14][15] group 12, [16] group 13, [17,18] group 14, [19,20,16] group 15, [21] group 16, [22,23] transition metals (V and Cr, [24] Mn [25,26] and Re, [27] Ru, Rh, Ir, [15,28,29] Os, [30] Co, [31] group 10: Ni, [32] Pd, [32,[33][34][35] Pt, [14,30,34] and group 11: [35] , and rare earth metals. [36,37] This could be due to the flexible nature of the ligand moieties, which adopt to several metallacyclic rings depending upon the coordination to the central metal atom. We had recently reported that the missing group 2 metal complexes of di-selenoimidodiphosphinato ligand by synthesizing strontium and barium complexes via two synthetic routes -using diselenoimidodiphosphinato ligand with either silylamide or the salt metathesis route).…”

Synthesis and structural studies of phosphorus carbonyl manganacycles containing the tetraphenyldiselenoimidodiphosphinato ligand

“…The fact is that coordination of the [N(EPPh 2 ) 2 ] À (E = O, S, Se) anions has been extensively studied over the last years. It has been found that the ligand N(SePPh 2 ) 2 binds a wide range of atoms varying from main group elements (K [2], group 12 [3]; Al and Ga [4], In [5], Sn [3,6], Pb [3], Sb [7], Bi [5,7], Se [8] and Te [9]), transition metals (V and Cr [10], Mn [11a] and Re [11], Ru [12], Os [13a,13b], Co [14], Rh [2,12b,12c], Ir [12b,15], group 10: Ni [16], Pd [2,12c,16,17], Pt [2,16,17], and group 11: Cu [14,18a] Ag [18a,18b,18c] Au [18b,18d,18e]) to rare-earth metals: Y [19], La, Gd, Er, Yb [20], and Sm [21]. Although the list of N(SePPh 2 ) 2 [22] complexes is certainly long, it is noteworthy the scarcity of metal carbonyl complexes with the N(SePPh 2 ) 2 fragment (or [N(EPPh 2 ) 2 ] À ; E = O, S for that matter).…”