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T. Ito, A. Yamamoto, et al., J. Chem. Soc., Chem. Commun., 136 (1974) J. Chem. Soc., Dalton Trans., 1783 (1974) J. Chem. Soc., Dalton Trans., 1398 (1975) 11

T.Ito, A. Yamamoto, et al., Bull. Chem. Soc. Japan, 49, 3250 (1976) Bull. Chem. Soc. Japan, 49, 3257 (1976) Chemistry Letters, 835 (1976) J. rganometallic Chem., 161, 61 (1978) J. rganometallic Chem., 174, 237 (1979) 12

1980 2004 M Ph 2 P PPh 2 Ph P P 2 Ph 2 C C M L Ph N N Ph 13

Periodic Table of Elements cd 1 2 e 2.1 1S 1 3 Li 1.0 2S 1 11 Na 1.0 3S 1 19 K 0.9 4S 1 37 Rb 4 Be 1.5 2S 2 12 Mg 1.3 3S 2 20 Ca 1.1 4S 2 38 Sr 21 Sc 1.2 3d 1 4S 2 39 Y 22 Ti 1.3 3d 2 4S 2 40 Zr 23 V 1.5 3d 3 4S 2 41 Nb 24 Cr 1.6 3d 5 4S 1 42 25 Mn 1.6 3d 5 4S 2 43 Tc 26 Fe 1.7 3d 6 4S 2 44 Ru 27 Co 1.7 3d 7 4S 2 45 Rh 28 Ni 1.8 3d 8 4S 2 46 Pd 29 Cu 1.8 3d 10 4S 1 47 Ag 30 Zn 1.7 3d 10 4S 2 48 Cd 5 B 2.0 2S 2 2p 1 13 Al 1.5 3S 2 3p 1 31 Ga 1.8 4S 2 4p 1 49 In 6 C 2.5 2S 2 2p 2 14 Si 1.8 3S 2 3p 2 32 Ge 2.0 4S 2 4p 2 50 Sn 7 N 3.1 2S 2 2p 3 15 P 2.1 3S 2 3p 3 33 As 2.2 4S 2 4p 3 51 Sb 8 3.5 2S 2 2p 4 16 S 2.4 3S 2 3p 4 34 Se 2.5 4S 2 4p 4 52 Te 9 F 4.1 2S 2 2p 5 17 Cl 2.9 3S 2 3p 5 35 Br 2.8 4S 2 4p 5 53 I 1S 2 10 Ne 2S 2 2p 6 18 Ar 3S 2 3p 6 36 Kr 4S 2 4p 6 54 Xe 0.9 5S 1 55 Cs 0.9 6S 1 1.0 5S 2 56 Ba 0.9 6S 2 1.1 4d 1 5S 2 La ~1.1 4f n 5d m 1.2 4d 2 5S 2 72 f 1.2 5d 2 6S 2 1.3 4d 4 5S 1 73 Ta 1.4 5d 3 6S 2 1.3 4d 5 5S 1 74 W 1.4 5d 4 6S 2 1.4 4d 6 5S 1 75 Re 1.5 5d 5 6S 2 1.4 4d 7 5S 1 76 s 1.5 5d 6 6S 2 1.5 4d 8 5S 1 77 Ir 1.6 5d 7 6S 2 1.4 4d 10 5S 0 78 Pt 1.5 5d 9 6S 1 1.4 4d 10 5S 1 79 Au 1.4 5d 10 6S 1 1.5 4d 10 5S 2 80 g 1.5 5d 10 6S 2 1.5 5S 2 5p 1 81 Tl 1.5 6S 2 6p 1 1.7 5S 2 5p 2 82 Pb 1.6 6S 2 6p 2 1.8 5S 2 5p 3 83 Bi 1.7 6S 2 6p 3 2.0 5S 2 5p 4 84 Po 1.8 6S 2 6p 4 2.2 5S 2 5p 5 85 At 2.0 6S 2 6p 5 5S 2 5p 6 86 Rn 6S 2 6p 6 87 Fr 0.9 7S 1 88 Ra 0.9 7S 2 Ac ~1.1 5f n 6d m 104 Rf 105 Db 106 Sg 107 Bh 108 s 109 Mt 110 Ds 57 La 58 Ce 59 Pr 60 Nd 61 Pm 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 p 68 Er 69 Tm 70 Yb 71 Lu 89 Ac 90 Th 91 Pa 92 U 93 Np 94 Pu 95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr 14

Ph 2 P Ph P 2 [] [] R R R P Ph 2 RC 1) - + [] PPh 2 2 [ ] = (dppe) 2 R R - 2 6) R - 2 [] = 4 (dppe) 2 hν - 2 R 8) R [] [] 2) C 2 RC 2 -N 10) -2 PhSi 3 2 Ph P Si 3,4) Ph P P 2 Ph 2 PPh - 2 [] R 5,9) X NRCR' - 2 R + 7) N [] N [] T. Ito, Bull. Chem. Soc. Jpn., 72, 2365-2377 (1999) R' X 1) T. Ito, A. Takahashi, S. Tamura, Bull. Chem. Soc. Japan, 59, 3489 (1986). 2) T. Ito, T. Matsubara, J. C. S., Dalton Trans., 2241 (1988). 3) T. Ito, et al., J. C. S., Dalton Trans., 1645 (1990). 4) T. Ito, T. Matsubara, Y. Yamashita, J. C. S., Dalton Trans., 2407 (1990). 5) S. Kurishima, T. Ito, et al., J. C. S., Dalton Trans., 1135 (1991). 6) T. Ito, et al., rganometallics, 5, 735 (1986). 7) T. Ito, S. Kurishima, et al., rganometallics, 11, 2333 (1992). 8) M. Minato, T. Ito, et al., Chem. Lett., 2339 (1994). 9) M. Minato, T. Ito, et al., rganometallics, 15, 4863 (1996). 10) D.-Y. Zhou, T. Ito, et al., Chem. Lett., 1017 (1997); 187 (1998). 15

R Si Ph 2 P Ph 2 P Si Ph P Ph 2 P P Ph PPh 2 Ph(R)Si 2, - 2 2 R=,Me,Ph 2 P Ph r.t., - 2 P Ph 2 Ph 2 P PPh 2 Ph 2 P P Ph 2 Si Ph P Ph 2 P PPh P Ph 2 PhSi 3 PhSi 3, - 2, - 3 2 RCN r.t., - 2 Si Ph P PPh Ph 2 P P Ph Si 2 2 :SiPh Si Ph P Ph 2 P C N R P Ph P Ph 2 R R RC, - 2 or C 2, - 2 r.t., - 2, - C 2 Si Ph P Si PPh Si Ph 2 P P Ph Ph P 2 P Ph P P Ph C 2 / 2 Ph Ph P 2 P Ph 2 Ph R 2 P PPh 2 C R R Ph Si n D.-Y. Zhou, T. Ito, et al., Chem. Lett., 1017 (1997) D.-Y. Zhou, T. Ito, et al., Chem. Lett., 187 (1998) T. Ito, K. Shimada, et al., J. rganomet. Chem., 611, 308 (2000) M. Minato, T. Ito, et al., Chem. Lett., 960 (2001) M. Minato, D.-Y. Zhou, T. Ito, et al., Chem. Comm., 2654 (2001) M. Minato, J. Nishiuchi, T. Ito, et al., JCS Dalton Trans. 483 (2003) M. Minato, T. Matsumoto, T. Ito, et al., Chem. Comm., 2968 (2003) C 16

17 dern Coordination Chemistry, The Legacy of Joseph Chatt, ed. by Leigh & Winterton

Chemistries of and W Complexes with Cp 2 M Fragments [Cp 2 Me ] + A - [Cp 2 ] + A - [Cp ] + A - 2 PPh 3 C Me PPh 3 C Cp 2 M 2 + A [Cp 2 M 3 ] + A - [Cp 2 ] + A - Me 2 C 2, R=Bu n Cp 2 PR 3 Cp 2 M - PR 3 [Cp ] + A - 2 PR3 or Ts Cp 2 M + MCp 2 + [Cp 2 2+ 2A - Cp 2 ] + A - - M=,W;Cp=η 5 -C 5 5, η 5 -C 5 4 Me; A = p-ts 18

Chemistries of and W Complexes with Cp 2 M Fragments Cp 2 2 + A 2 C E,A Cp 2 A 2 [Cp 2 3 ] + A - 2 C E E=orNR Cp 2 2 + CE + A Cp 2 ()A + C E Cp 2 ()A + CE + A Cp 2 A 2 + C E Path (A) Cp 2 (A) + A CE A Cp 2 CE + A- A Cp 2 C E + A- CE Cp 2 A 2 Path (B) Cp 2 (A) + A CE A Cp 2 E C + A - A Cp 2 E + A- CE Cp = η-c 5 5 A = p-ts, C 3 C, or C 3 19 cf. T. Ito et al., J. C. S. Chem. Commun., 1990, 988

Chemistries of and W Complexes with Cp 2 M Fragments Synthesis and Crystal Structure of N-eterocyclic Carbene Complexes of Bis(η 5 -cyclopentadienyl)molybdenum N-eterocyclic carbene complexes of molybdenocene (3), which are prepared by the reaction of an imidazolium salt with either [(η 5 -C 5 5 ) 2 ()(Ts)] (1) or [(η 5 -C 5 5 ) 2 ()Li] 4 (6-), were characterized by spectroscopic analyses as well as by an X-ray structure determination. Y. Yamaguchi,* R. da, K. Sado, K. Kobayashi, M. Minato and T. Ito* [Cp 2 ()(Ts)] cationic molybdenocene 1 1/4 [Cp 2 ()Li] 4 anionic molybdenocene 6- imidazolium salt base imidazolium salt hν R N C N R R = i Pr, Me, Mes 3 Bull. Chem. Soc. Jpn., 76 (5), 991-997 (2003) 20

P. J. Chirik, et al., Nature, 427, 527 (2004) C&E News, Feb. 9, 2004 21

( 301 ) 303 (M)- (C) (2001 ) (2000 ) 22

C 3 C 2 C n C C 2 R 1966 1970 R = N -C 2 C 3, -(C 2 ) 2 C 3, -(C 2 ) 3 C 3, -C 2 SC 3, -C 2 N(C 3 ) 2, S Ph 3 P Ph 3 P 1970 N N Ru PPh 3 R 3 P R 3 P W PR 3 PR 3 Cl Cl 1972 1975 PPh 3 s PPh 3 N R C N 23 R'

Ph 2 Ph 2 P P PPh 2 P Ph 2 3 C 3 C 3 C Pt C 3 PR 3 C 3 C R C C 3 2 C C 2 C PPh 2 PPh 2 Ph 3 P C P P Ru Ph 2 Ph 2 Ph 3 P PPh 3 1974 1975 1976 C 3 3 C Et 3 P C C CC 3 Pt 3 CC PEt 3 C C C 3 1976 1979 C 3 C C 3 N Pt N C 3 C 3 C R 3 P C 2 C 3 Pd Pd R 3 P C 3 C 2 PR 3 PR 3 24

MePh 2 P MePh 2 P Pd R R R = Me, Et, n-pr Et 3 P R Pd R PEt 3 1976 1977 Ph 2 MeP Ph 2 MeP Pd = C 3 Ph CMe CMe C 3 CN MeC CMe 1979 1981 Ph 3 P PPh 3 Rh PPh 3 C Rh PPh 3 PPh 3 2RC Ru 2 (PPh 3 ) 4 RC 2 C 2 R 1976 1978 1982 25

3 C 3 C Cr C 3 C 3 Cy 3 P Mn Cy 3 P Mn C C Et 3 P Fe Et 3 P 1975 1982 3 C 3 C 3 C PEt 3 Co PEt 3 3 C Ph 3 C C Ph Ni Ni PR 3 PR 3 3 C R = Ph, Cy, Et 26

3 C C C X + Rh(PPh 3 ) 4 Rh X =, C Ph 3 P 3 PPh 3 + C 4 + 2 PPh 3 X 1982 Ph 3 P Ph 3 P Co PPh 3 N N Mg N NCo PPh 3 Ph 3 P Et 2 Ph 3 P Co N N Li Et 2 Ph 3 P PPh 3 Ph 3 P Et 2 1983 27

M + M M Ts W CR CR M CR W C C C M C C C C M W R + PR 3 PR 3 + + + + + M M M R' PR 3 28

PPh 2 PPh 2 Ph 2 P R Ph 2 P NC C Ph C 2 P C N 2 PPh 2 PPh 2 C 3 Ph 2 P PPh PPh 2 2 PPh Ph P 2 2 Ph Ph 2 P 2 P N 2 + Ph 2 P C R C R CN PPh 2 Ph Ph 2 P 2 P Ph 2 P Ph 2 P PPh 2 PPh 2 PPh 2 R C C C PPh 2 R PPh 2 Ph 2 P N Ph 2 P PPh 2 C C E PPh 2 Ph 2 P N Ph 2 P PPh 2 X PPh 2 Ph 2 P C R 2 Ph N 2 P PPh R 1 2 PPh Ph 2 2 Ph 2 Ph P P P 2 P P Ph Ph 2 P 3 C C 2 3 PPh 2 R R Ph Si P P Ph Si R Si Ph Si Si Ph P PPh 2 P P Ph P PPh Ph Ph P P Ph Ph 2 P P Ph 2 P P Ph 2 P P Ph P Ph 2 P P Ph 2 P Ph 2 I Ph 2 2 Ph2 Si Ph 2 2 Si Ph P Ph 2 P R PPh PPh 2 R Si Ph P Ph 2 P 3 C P Ph PPh 2 C 3 Si Ph P PPh Ph 2 P P Ph 2 C R Ph 2 P Ph 2 P Ph 2 P P Ph 2 29

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FD Jon Dilworth 47