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H. Nmr, 6 (s, N=P), ?3.4 (s, PEt 3, ?144.8 (h, 1 J PF = 710 Hz

. Anal, Calcd for C 49 H 52 CuF 6 N 3 P 4 : C, 59.79; H, 5.32; N, 4.27. Found: C, 59.65; H, 5.32, ? Compound [L Ph CuBr 2 ] Formula: C 43 H 37 Br 2 CuN 3 P 2 Molecular weight, pp.881-889

C. Hz, 6 (d, 1 J PC = 61

L. Aspect and . Me, 5 mg, 86 µmol) and YbI 2 (86 µmol, 18.3 mg) were stirred in THF (2 mL) for 15 minutes, then Et 2 O (5 mL) was added to enhance the precipitation. The mixture was then centrifuged. The supernatant was removed and Et 2 O (5 mL) was added, the mixture was stirred for 5 minutes and centrifuged again, the supernatant was removed and the solid was dried under vacuum overnight to yield [L Me 2 Yb]I 2 (46.2 mg, 94 %) as a green powder, pp.31-32

. Anal, Calcd for C 26 H 50 I 2 N 6 P 4 Yb: C, 31.31; H, 5.05; N, 8.43. Found: C, 31.41; H, 5.18, ? Compound [L Me 2 Sm]I 2

. Mg, 59 µmol) yielding [L Me 2 Sm]I 2 as a yellowish powder (53.1 mg, 92 %)

L. Aspect and . Ph, 5 mg, 0.18 mmol) and [UI 3 (THF) 4 ] (162 mg, 0.18 mmol) were stirred in THF (10 mL) for 5 hours. The solvent was then removed under vacuum Then toluene (2 mL) and pentane (5 mL) were added to form a deep blue precipitate. The mixture was filtered and washed pentane (2x3 mL) and toluene (1 mL). The solid was dried under vacuum for 3 hours to yield [L Ph UI 3 ] (96.0 mg, 74 %) as a blue powder, pp.31-32

L. Aspect and . Cy, 8 mg, 80 µmol) and [UI 3 (THF) 4 ] (73 mg, 80 µmol) were stirred in a mixture of Et 2 O and THF (5 mL/1 mL) overnight, resulting in the formation of a blue precipitate. The solid was filtered, washed with Et 2 O (2x3 mL) and finally dried under vacuum for 3 hours to yield

. Anal, Calcd for C 43 H 75 I 3 N 3 P 2 U: C, 39.34; H, 5.61; N, 3.20, pp.812-97

L. Aspect and . Cy, 127 mg, 0.18 mmol) and [Yb(tmp) 2 (THF)] (96 mg, 0.18 mmol) were stirred in Et 2 O (2 mL) for 3 h leading to the formation of a green precipitate, pentane (10 mL) was added to enhance the precipitation and the mixture was centrifuged and stored at -40°C overnight. The liquid was removed and the operation repeated another time with 10 mL of pentane. Finally the dark green solid was dried under high vacuum for 2 h to yield

C. Hz, 5 (s, C 8 )

. Anal, Calcd for C 59 H 97 N 3 P 4 Yb: C, 61.87; H, 8.54; N, 3.67. Found: C, 61.63; H, 8.62, ? Compound [L Me 2 Yb](tmp

L. Aspect and . Me, 1 mg, 0.20 mmol) and [Yb(tmp) 2 (THF)] (51.6 mg, 0.10 mmol) were stirred in toluene (2 mL) for 1 hour, then Et 2 O (2 mL) was added and the mixture was triturated with a spatula to form a green precipitate. The mixture was then centrifuged. The supernatant was removed and a mixture of Et 2 O and pentane (2 mL/2 mL) was added, the mixture was stirred for 5 minutes and centrifuged again, the supernatant was removed and the solid was dried under vacuum overnight to yield) as a green powder, pp.31-32

. Aspect, mg, 1.99 mmol) was dissolved in diethyl ether (15 mL) PPh 3 (522 mg, 1.99 mmol) was added as a solid After few seconds, a nitrogen evolution was potent, the mixture was stirred for 5 h at room temperature. The solvent was evaporated under reduced pressure; the resulting yellow oil was washed with petroleum ether to yield 3 as a yellow viscous oil

. Aspect, The red mixture of the anion was stirred for 5 min at -78°C and then at 0°C for 15 min Both Schlenk flasks were cooled to 0°C and the mixture of the anion was added via cannula to the other flask in about 20 min (ca. 1 drop/second). The mixture was then stirred at 0°C for 1h. Solvents were then evaporated to give an off-white solid which was then suspended in pentane

. Ml, After filtration and washing with pentane (5 mL), an off-white solid was obtained (1.03 g, 90 %)

. Anal, 12; N, 6.34. Found: C, 65.33; H, 10.22; N, 5.25. filtered and Et 2 O (20 mL) was added leading to the precipitation of a yellowish solid. The precipitate was filtered and washed with Et 2 O (10 mL) After drying under vacuum, Pd(py)](BF 4 ) 2 (72.1 mg, 60%) was isolated

C. Hz, 6 (d, 1 J PC = 42 (s, C ? ), pp.122-127

. Hz, 85 (s, C 6 )

1. Hz, 25 (d, 3 J HH = 6.6 Hz, 1H

. Aspect, 30 mg, 44 µmol) and B(C 6 F 5 ) 3 (22.4 mg, 44 µmol) were suspended in toluene (3 mL) After 3 hours of stirring the mixture turned clear and was checked in 31 P{ 1 H} probing the disappearance of the starting material and the formation of a new product characterized by a doublet of doublet at 47.1 ppm (J = 23.0, 7.5 Hz) and a doublet at 31.1 ppm (J = 7.5 Hz). The mixture was then transferred to a Schlenk flask and the volatiles were removed under vacuum. The solid was then suspended in pentane (3 mL, filtered, then the solid was washed with Et 2 O (1 mL) and pentane (2x3 mL) to give an off-white solid which was dried under high vacuum to furnish [L 1B PdMe] (39

H. Nmr, 1 (dd, J = 22

2. and H. Ar, 73 (d, 3 J HH = 7.3 Hz, 1H, pp.29-35

H. Nmr, Tol-d 8 ) ? 54.0-52.8 (m, N=PCy 3 and PPh 2 )

1. Hz, J. Hh, 3. Hzm, and . Cy, 34 (m Even at low temperature, signals remained very broaden and do not allow the accurate determination of the coupling constants, pp.35-35

. Aspect, KHMDS (8 mg, 40 µmol) and [L 1 RuCl 2 (PPh 3 )] (20 mg, 40 µmol) were mixed in THFd 8 (0.75 mL) and stirred for 5 minutes. The solution was filtered and transferred to a J-Young NMR tube for spectroscopic analysis

1. Hz and 1. , 23 (d, 3 J HH = 6.4 Hz, 1H, ABX system (3.95 J HH = 14.9 Hz, 3 J PH = -5.9 Hz, 1H, pp.70-71

. 6h, 40 (bd, 3 J HH = 7.6 Hz, p.35

1. Hz, 12 (d, 3 J HH = 7.2 Hz, 1H

1. Hz, 69 (ABX system, dd, 2 J HH = 15.3 Hz, 3 J PH = 11.6 Hz, 1H, H 6b )), AMX system2, p.69

J. Pc-=-9, At least 20 others signals in the aromatic region can be detected but not assigned, J PC ca, vol.127, issue.478 6, pp.1403-97

. Aspect, 8 mg, 78.5 µmol) and KHMDS (31.4 mg, 157 µmol) were stirred in benzene (3 mL) for 20 minutes resulting in a brown solution. A suspension of [UI 4 (dioxane) 2 ] (72.4 mg, 78.5 µmol) in benzene (5 mL) was added resulting in a color change to brown. The mixture was stirred for 2 hours at room temperature. The mixture was filtered over a pad of celite which was washed with toluene (3 mL). The volatiles were evaporated and the resulting yellow powder was suspended in pentane (5 mL) After filtration, the powder was washed with pentane, mL) and dried under vacuum for 2 hours to yield [L Salen UI 2 ] (103 mg, 93 %)

. Aspect, 1 mg, 0.025 mmol) and KHMDS (102 mg, 0.51 mmol) were stirred in THF (12 mL) for 2 hours resulting in a brown solution. A suspension of [UO 2 Cl 2 (THF) 2 ] (123.7 mg, 0.25 mmol) in THF (4 mL) was added resulting in a color change to red. The mixture was stirred for 2 hours at room temperature. The mixture was filtered over a pad of celite and dried under vacuum. The red/orange powder was suspended in pentane (15 mL) After filtration, the solid was washed with pentane (10 mL) and finally extracted with DCM (10 mL)

C. Hz, 0 (s, 1 J PC = 126.6 Hz, pp.31-39

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