Bis(cyclopentadienyl)yttrium Complexes of the Ligand [N(QPPh₂)₂]^- (Q = S, Se):  Synthesis, Structure, and NMR Properties of Cp₂Y[η³-N(QPPh₂)₂]

Abstract

The compounds Cp(2)Y[eta(3)-N(QPPh(2))(2)] (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reaction between Cp(3)Y and HN(QPPh(2))(2) in tetrahydrofuran. In both compounds, the [N(QPPh(2))(2)](-) ligand is bound eta(3) to the Y center which, in 1, represents the first example of that mode of binding for the sulfur-containing ligand. The Y atom is also coordinated to two (C(5)H(5))(-) ligands and so is formally 9-coordinate. Both 1 and 2 are stable in inert environments for prolonged periods of time. Each is soluble in THF and CH(2)Cl(2). (1)H, (31)P, (77)Se, and (89)Y NMR data were collected to lend insight into the solution properties of these molecules. Crystallographic data for 1 (-120 degrees C): C(34)H(30)NP(2)S(2)Y, triclinic, P&onemacr;, a = 9.685(5) Å, b = 12.176(6) Å, c = 13.978(7) Å, alpha = 87.382(9) degrees, beta = 87.358(9) degrees, gamma = 68.689(9) degrees, V = 1533(1) Å(3), Z = 2, and R(1)(F) = 0.047 for the 4023 reflections with I > 2sigma(I). Crystallographic data for 2 (-120 degrees C): C(34)H(30)NP(2)Se(2)Y, triclinic, P&onemacr;, a = 9.745(5) Å, b = 12.222(6) Å, c = 13.930(7) Å, alpha = 88.024(9) degrees, beta = 87.380(9) degrees, gamma = 69.137(9) degrees, V = 1548(1) Å(3), Z = 2, and R(1)(F) = 0.056 for the 4324 reflections with I > 2sigma(I).

Synthesis and Characterization of HN(SPiPr2)(SePPh2) and [Te{N(SPiPr2)(SePPh2)}2]

“…The 31 P{ 1 H} NMR spectrum of HN(SP i Pr 2 )(SePPh 2 ) shows two doublets with the expected 77 Se satellite and 2 J P - P coupling of 28 Hz. The P−Se coupling constant, 1 J P - Se , in HN(SP i Pr 2 )(SePPh 2 ) is consistent with values found in other systems containing the Ph 2 P(Se) fragment and hence with the presence of a PSe double bond. , The 31 P{ 1 H} NMR spectrum of [Te{N(SP i Pr 2 )(SePPh 2 )} 2 ] recorded at 25 °C shows two sets of doublets with equal 2 J P - P coupling of 25 Hz, indicative of the presence of two isomers (cis and trans). The 77 Se NMR spectrum of [Te{N(SP i Pr 2 )(SePPh 2 )} 2 ] displays two doublets with different 1 J Se - P coupling constants.…”

“…A number of bis-S or bis-Se compounds HN(QPR 2 ) 2 (Q = S, Se; R = Me, Et, Ph, i Pr, n Bu, OPh) have been synthesized, and the coordination chemistry of their anions [N(QPR 2 ) 2 ] - has been extensively studied with a variety of transition-metal, main-group, and rare-earth systems. − In addition, the unsymmetrical bis-S compounds HN(SPR 2 )(SPR‘ 2 ) (R = Ph, R‘ = Me, Et, i Pr, OEt, OPh; R = OPh, R‘ = Et, i Pr, OEt) have been prepared and their anions complexed with Co, Zn, Pd, and Pt systems. − …”

PCP-bridged chalcogen-centred anions: coordination chemistry and carbon-based reactivity

“…By contrast, N-coordination is observed only rarely for metal complexes of 1, notably the lanthanides. 8…”

Dioxo- and nitrido-osmium complexes with imidodiphosphinochalcogenido ligands [N(QPR2)2]− (Q = S or Se; R = Ph or Pri)

“…The monoanions imidodiphosphinochalcogenides [N(QPR 2 ) 2 ] Ϫ (Q = chalcogen, R = alkyl or alkoxy) are known to bind to p-, d-, and f-block metal ions exhibiting rich structural diversity. [1][2][3][4] These ligands are of interest due to their uses as lanthanide NMR shift reagents 5 and catalysts. 6 Owing to the convenient synthetic routes to HN(QPR 2 ) 2 and related compounds developed by Woollins and co-workers, 7 the co-ordination chemistry of imidodiphosphinochalcogenides has become an active area of investigation as exemplified by the plethora of publications reported in the last few years.…”

“…6 Owing to the convenient synthetic routes to HN(QPR 2 ) 2 and related compounds developed by Woollins and co-workers, 7 the co-ordination chemistry of imidodiphosphinochalcogenides has become an active area of investigation as exemplified by the plethora of publications reported in the last few years. [1][2][3][4] There are, however, relatively few studies on their complexes with Group 8 transition metals, particularly osmium. 3,8, 9 The only isolated osmium complexes with [N(QPR 2 ) 2 ] Ϫ ligands are the sulfide complexes [Os 3 (CO) 10 {Ph 2 P(SH)NP(S)Ph 2 -S,S}] and [Os 3 H(CO) 9 {Ph 2 P(S)NP(S)Ph 2 -S,S}], which were synthesized from [Os 3 (CO) 11 (MeCN)] and HN(SPPh 2 ) 2 , 10 and the nitridoosmium() complex [OsN{N(SPPh 2 ) 2 } 2 X] (X = Cl or CF 3 CO 2 ).…”