REACTIVITY OF HYDRAZINES WITH ORGANOMETALLIC SAMARIUM COMPLEXES AND THE X-RAY CRYSTAL-STRUCTURES OF (C5ME5)2SM(ETA-2-PHNHNPH)(THF), (C5ME5)2SM(NHPH)(THF), AND [(C5ME5)2SM]2(MU-ETA-2-ETA-2-HNNH)(1)

(C5Mes)2Sm(THF)2 reacts with PhNHNHPh in hexane to cleave the NN bond and form (CsMe5)2Sm(NHPh)(THF) (1) in 80% yield. The coordinated THF can be removed from 1 by heating to 90-degrees-C at 2 x 10(-6) Torr for 2 h, which sublimes [(C5Me5)2SM(NHPb)]x (2). Addition of THF to 2 regenerates 1 quantitatively. 2 can also be synthesized from the reaction of[(C5Me5)2Sm(mu-H)]2 and PhNH2. NN bond cleavage is not observed, however, when (C5Me5)2Sm reacts with PhNHNHPh. This reaction forms a complex, 3, which can be isolated as the THF adduct (C5Me5)2SM(eta-2-PhNHNPh)(THF) (4), in which the NN bond is retained. 3 can also be obtained from the reactions of [(CsMe5)2Sm(mu-H)]2 with either PhNHNHPh or PhN=NPh as well as from reactions of PhNHNHPh with [(C5Me5)2SM]2(mu-PhNNPh) and (C5Me5)2Sm(PhNNPh)(THF). The reaction of excess [(C5Me5)2Sm(mu-H)]2 with PhNHNHPh for MS[(C5Me5)2Sm]2(mu-PhNNPh). [(C5Me5)2Sm(mu-H)]2 reacts with H2NNH2 in hexane to for [(C5Me5)2Sm]2(mu-eta-2:eta-2-HNNH) (5) in 60% yield. 5 can also be prepared from (C5Me5)2Sm and H2NNH2. 1 crystallizes from THF in space group P2(1)/c with a = 19.052 (2) angstrom, b = 8.484 (1) angstrom, c = 18.572 angstrom, beta = 113.30 (1)-degrees, V = 2757.0 (6) angstrom3, and D(cald) = 1.41 g CM-3 for Z = 4. Least-squares refinement of the model based on 6059 reflections (\F(o)\ > 0) converged to a final R(F) = 3.7%. 4 crystallizes from hexane at -35-degrees-C in space group P2(1)c with a = 9.811 (2) angstrom, b = 16.098 (5) angstrom, c = 23.393 (7) angstrom, beta = 99.20 (2)-degrees, V= 3647 (2) angstrom3, and D(cald) = 1.31 g cm-3 for Z = 4. Least-squares refinement of the model based on 4380 reflections ([F(o)\ > 1.0-sigma(\F(o)\)) converged to a final R(F) = 4.6%. 5 crystallizes from hexane at -35-degrees-C in space group P2(1)/c with a = 11.0827 (13) angstrom, b = 14.398 (2) angstrom, c = 25.895 (3) angstrom, beta = 93.324 (10)-degrees, V = 4125.1 (9) angstrom3, and D(cald) = 1.47 g cm-3 for Z = 4. Least-squares refinement of the model based on 5824 reflections (\F(o)\ > 3.0-sigma(\F(o))) converged to a final RF = 3.3%. The arrangement of the four ligands in both (C5Me5)2Sm(NHPh)(THF)(1) and (C5Me5)2Sm(eta-2-PhNNHPh)(THF) (4) can be roughly described as distorted tetrahedral. Sm-N bond distances are 2.331 (3) angstrom (Sm-NHPh) in 1 and 2.330 (5) angstrom (Sm-NPhNHPh) and 2.610 (5) angstrom (Sm-NHPhNPh) in 4. The four C5Me5 rings in [(C5Me5)2SM]2(mu-eta-2:eta-2-HNNH) (5) form a tetrahedral cavity typical of complexes containing two (C5Me5)2SM units. However,the mu-eta-2:eta-2-HNNH ligand is located in a surprisingly off-center position in the cavity with Sm-N distances of 2.314 (4), 2 316 (4), 2.403 (4), and 2.436 (4) angstrom.