Bridge cleavage reactions of late transition-metal dimers with [Ph2P(E)NP(E′)Ph2]− (E = E′ = S or Se; E = O or S, E′ = S or Se)

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

“…This shift moves the resonances closer to the 31 P resonances in the K + salt of the ligand (Table ). The same trend is seen in the 31 P NMR spectra of other metal(III) complexes of the ligand: Sb[N(SePPh 2 ) 2 ] 3 (25.4 ppm), Bi[N(SePPh 2 ) 2 ] 3 (27.3 ppm), In[N(SePPh 2 ) 2 ] 3 (28.5 ppm), and [RuCl{N(SePPh 2 ) 2 }(η 6 - p -MeC 6 H 4 Pr i )] (29.0 ppm) . The ligands in these species are Se, Se‘-coordinated.…”

“…The bite angle (Q(1)−Y(1)−Q(2)) of the η 3 -coordinated [N(QPPh 2 ) 2 ] - ligand is substantially larger than that of the η 2 -coordinated ligand. For example, this angle is 126.94(4)° in 1 , 129.54(3)° in 2 , and 125.39(4)° in [Sm{η 2 -N(SePPh 2 ) 2 {η 3 -N(SePPh 2 ) 2 (THF) 2 ], the only other example of η 3 -bonding, whereas representative bite angles in Q,Q‘-coordinated complexes are 101.27(3)° in [Pd(C 9 H 12 N){N(SePPh 2 ) 2 }], 99.7(1)° in [Pt(C 8 H 12 OMe){N(SPPh 2 ) 2 }], and 92.51(4)° in [Sm{η 2 -N(SPPh 2 ) 2 } 2 (THF) 2 ] …”

“…In 1995, Bhattacharyya and co-workers 9-12,17 reported a convenient preparation of these ligands that facilitated these studies. These ligands are known to exhibit a range of binding geometries that depend on the choice of Q, R, and chelated metal. ,, For example, [N(SePPh 2 ) 2 ] - forms neutral square-planar complexes with Pd(II), Pt(II), and Ni(II) with chelation of the two Se atoms to the metal. , Surprisingly, though, the neutral Ni(II) complex of [N(SP i Pr 2 ) 2 ] - has a tetrahedral geometry . The Q,Q‘-chelation mode that uses both chalcogen donor atoms is well-represented. ,,− A variety of other bonding motifs have been found with imidodiphosphinochalcogenido ligands, including multimetallic cluster compounds with bridging ligands. ,,

1

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“…The inorganic ligands imidodiphosphinochalcogenido, [N(QPR 2 ) 2 ] -(Q ) S, Se; R ) Me, Ph, Et for example), have recently been the focus of many studies [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] (Scheme 1) owing to the structural diversity in the metal complexes they form and their relationship to the organic ligand acetylacetonato (acac). In 1995, Bhattacharyya and co-workers [9][10][11][12]17 reported a convenient preparation of these ligands that facilitated these studies. These ligands are known to exhibit a range of binding geometries that depend on the choice of Q, R, and chelated metal.…”

“…These ligands are known to exhibit a range of binding geometries that depend on the choice of Q, R, and chelated metal. 9,15,17 For example, [N(SePPh 2 ) 2 ]forms neutral squareplanar complexes with Pd(II), Pt(II), and Ni(II) with chelation of the two Se atoms to the metal. 12,19 Surprisingly, though, the neutral Ni(II) complex of [N(SP i Pr 2 ) 2 ]has a tetrahedral geometry.…”