Bridging μ‐η⁵:η⁴‐Coordination of an Indenyl Ligand and Reductive Coupling of Diazabutadienes in the Assembly of Di‐ and Tetranuclear Mixed‐Valent Ytterbium Indenyldiazabutadiene Complexes

Abstract

The redox reaction of [Yb(C(9)H(7))(2)(thf)(2)] with the diazabutadiene PhN==C(Me)--C(Me)==NPh (DAD) has been found to depend on the molar ratio of the reactants. Reaction in a 1:2 molar ratio affords the dinuclear mixed-valent complex [Yb(2)(mu-eta(5):eta(4)-C(9)H(7))(eta(5)-C(9)H(7))(2){mu-eta(4):eta(4)-PhNC(Me)==C(Me)NPh}] containing an indenyl ligand with an unusual mu-eta(5):eta(4) bridging coordination. Reaction of equimolar amounts of these compounds results in an organolanthanide-mediated reductive coupling of the DAD ligands and formation of the tetranuclear mixed-valent complex [Yb(2)(mu-eta(5):eta(4)-C(9)H(7))(eta(5)-C(9)H(7))(2){mu-eta(4):eta(4)-PhNC(CH(2))==C(Me)NPh}](2) with a novel tetradentate tetraimine ligand.

Europium bis(dimethylsilyl)amides including mixed-valent Eu3[N(SiHMe2)2]6[μ-N(SiHMe2)2]2

“…Two of these (A, B) are oriented in the same direction while the third (C) is related to the former two by an inversion center. 31 Divalent Ln[N(SiMe 3 ) 2 ] 2 (thf ) 2 (Ln = Sm, Eu, Yb) and a tridentate amine bis( phenol) reacted to produce another example of mixed-valency (Sm III 2 Sm II L 4 ), while europium and ytterbium stayed in their divalent oxidation state. The central europium atom (Eu c ) of each molecule is coordinated by four bridging nitrogen atoms (N b ) from four [N(SiHMe 2 ) 2 ] − ligands in a distorted tetrahedral fashion.…”

Reactivity of the metal–cyclopentadienyl (indenyl, fluorenyl and cycloheptatrienyl) bonds

“…For the complexes L 2 Yb(THF) 2 (L = C 13 H 9 , C 5 Me 5 ), the same reaction results in an oxidative cleavage of the g 5 Yb-L (L = C 13 H 9 , C 5 Me 5 ) bond and formation of [Yb{2,6-i Pr 2 C 6 H 5 NCH(C 5 H 4 N) ÅÀ } 3 ] and [Yb(C 5 Me 5 ) {2,6-i Pr 2 C 6 H 3 NCH(C 5 H4N) ÅÀ } 2 ], respectively. ð11Þ Yb(C 9 H 7 ) 2 (THF) 2 reacts with PhN@C(Me)C(Me)@ NPh to give mixed-valent Yb 2 (l-g 5 :g 4 -C 9 H 7 )(g 5 -C 9 H 7 ) 2 {l-g 4 :g 4 -PhNC(Me)@C(Me)NPh} with a l-g 5 :g 4 -indenyl bridge or the coupling product of DAD ligands, [Yb 2 (l-g 5 :g 4 -C 9 H 7 )(g 5 -C 9 H 7 ) 2 {l-g 4 :g 4 -PhNC(CH 2 )@C(Me) NPh}] 2 , depending on the molar ratio of the reactants (Scheme 17) [57].…”

Electronic and Geometric Structures of Paramagnetic Diazadiene Complexes of Lithium and Sodium

“…[1][2][3] The list of stable DAD complexese ncompasses main-group metals, [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] early [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] and late [36][37][38][39][40][41][42][43][44][45][46][47] transition metals, as well as the lanthanides anda ctinides. [48][49][50][51][52]…”