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1 Organometallic Chemistry Introduction of Organometallic ChemistryTo m o a k i Ta n a s eNara Women s UniversityOrganometallic Chemistry1. Organometallic Compounds (Complexes)Organometallic Chemistry Zeise [PtCl3(C2H4)]- (0) [Ni(CO)4] 1951 Fischer Wilkinson [Fe(C5H5)2] 1973 (Organometallic Compound) P S (Organometallic Chemistry) NMR MLHard AcidHard BaseMLSoft AcidSoft BaseOrganometallic Chemistry 1950 1827 Zeise PtClClClCH2CH2-K[ Pt Cl3(CH2CH2)]1825 1828 1869 Mendeleev 1837 1848 1859,1860 AlRRRAlRRRAlR3 (R = Me, Et)1863 SiR4 ZnEt21900 Grignard R-Mg-X1912 1890 L.

2 MondNiOCOCCOCO[Ni( CO)4]1938 Roelen CoCoOCOCCOCOCOOCOCOC[Co2(CO)8] 1939 Reppe 1925 Fischer-Tropsh Organometallic Chemistry 1950 1950 1951 Pauson, Nature 1951, 168, 1039G. Wilkinson, R. B. Woodward, J. Am. Chem. Soc., 1952, 74, 2125E. O. Fischer, Z. Naturforsh 1952, 1954 FeWilkinson, Fischer 1951 Dewar, Chatt, Duncanson 1953 Ziegler 1959 Natta 1963 1964 Fischer 1970 Schrock 1965 Allen, Senoff Ru-NN1967 A. Yamamoto Co-NN1969 J. Chatt; M. Hidai Mo-NN 1961 Vaska 1965 Wilkinson ~1980 ~1980 1980 Sharpless1980 Bisnich Chiraphos1980 Noyori, Takaya BINAP2001 1970~1980 2000 1980 R.

3 West Si-Si 1971 Monsanto 1957 Wacker 1956 1957 Shirakawa2005 Ni 1972 (Kumada,Tamao,Corriu)Pd (1971 Mizorogi, 1972 Heck)1975 Sonogashira etc 1977 Negishi(1977 Migita, Kosugi), 1978 Stille)1979 (Suzuki, Miyaura)2010 1973 1981 R. Hoffmann Organometallic Chemistry2. Basic Principles for Organometallic CompoundsOrganometallic Chemistry 18 EAN (effective atomic number) 18 2 x 9 = 18 HOMO-LUMO (EAN) 1920 N.

4 V. Sidgwick) n = 2 HOMO-LUMO nd, (n+1)s, (n+1)p 9 Organometallic Chemistry (Td) (Oh) n 9-n 18 n Organometallic Chemistry 18 (D4h) Organometallic Chemistry Organometallic Chemistry Organometallic Chemistry Covalent methodIonic method Organometallic Chemistry hapticity) n (hapticity) n n bridge) n n (bridge)

5 2 5 3 1 2 3 Organometallic Chemistry Organometallic Chemistry Organometallic Chemistry Organometallic Chemistry Organometallic Chemistry Organometallic Chemistry [Fe(C5H5)2] [Co(C5H5)2] [Co(C5H5)2] FeCo[Fe(C5H5)2] [Co(C5H5)2] 8 (Fe) + 5 (h5-C5H5) x 2 = 18 9 (Co) + 5 (h5-C5H5) x 2 = 19 (Fe(II), Co(II)) [Co(C5H5)2]+ 8+5 x 2 = 189+5x2=19-e-Co9+5x2-1=18 Organometallic Chemistry (VEC) (EAN) (1) [Co(NH3)6]3+(2) [Cr(NH3)6]3+(3) [Zr( 5-C5H5)2Cl2] (4) [Mo( 5-C5H5)2H2](5) [Fe(CO)5] (6) [Ni( 5-C5H5)NO] (7) cis-[PtCl2(NH3)2] (8) [ReH9]2-(9) trans-P,P-[IrCl(I)(CH3)(CO)(PPh3)2] (10) [Ru(C CPh)( 5-C5H5)(PPh3)]

6 2]<Covalent method> M-M Ionic method Covalent method <Ionic method> 1 1 Organometallic Chemistry Cr, Mn, Fe, Co, Ni Cr Ni CO d d OCCrOCCOCOOCCOOCFeCOCOOCCOOCNiCOCOOCOCMn OCCOOCCOOCCoOCOCCOOCMnOCCOOCCOOCMnCOCOOC COO rganometallic Chemistry (VEC) (EAN) (1) [Ru3(CO)12] (2) [Co4(CO)12](1) [Rh2( 5-C5H5)2( -CO)2] (2) [Ru(CHPh)(Cl)2(NHC)

7 ]RuRuRuCOCOCOCOCOCOCOCOCOOCOCOCCoCoCoOCC oCOCOOCCOOCCOCOOCOCCOOCO rganometallic Chemistry FeZrCH3Cl-I-I-I-I-I-ICp-Cp-Cp-Cp-Cl-CH3- +II+IV -1 (Ionic method Organometallic Chemistry 18 5 [V(CO)6] (17e), [W(CH3)6] (12e), [Cr(Cp)(CO)2(PPh3)] (17e) 9, 10 d8 16 Pt(II), Pd(II), Ir(I), Rh(I) Organometallic Chemistry3. Representative LigandsOrganometallic Chemistry3 COCO HOMOLUMOMM MCO( donation)COM MCO( back donation)COMCO HOMO LUMO CO d CO (back donation) CO Organometallic Chemistry MCO( back donation) M-C C-O M-C C-O IR (CO) CO 2143 cm-1[Mn(CO)6]+ 2090[Cr(CO)6] 2000[V(CO)6]- 1860[Ti(CO))

8 6]2- 1750 3 MCOmonodentate2050-1900 cm-1 2-CO1900-1850 3-CO1800-1600 MMCOMMMCO Organometallic Chemistry trans effectMCOLMCOL C-O M-C C-O M-C IR (CO) NO+ > CS > CO > RNC > PF3 > PCl3 > PClR2 > P(OR)3 > PR3 > RCN > NH33 Organometallic ChemistrySynergic Bonding Dewar-Chatt-Duncanson Model HOMO (a1) LUMO (b2) MCCRRRR MCCRRRR CCCCa1b2 MMCC donation CC back donationMM3 Organometallic Chemistry MCMCCMCCMsp3sp2sp2alkyl complexalkenyl complexaryl complexalkynyl complex(acetylide complex) MCM CMC MC MC +-+- - 120~350 kJ/molC-C 347 kJ/mol3 Organometallic Chemistry MCABsp22e donorMCQR'RQR' = OR, NHR (carbene complex)MCRR' (alkylidene complex)R, R' = R, HFischer (1964)MCOR'RMCOR'RMCOR'RelectrophilicMCR R'MCRR'nucleophilicSchrock (1970)3 Organometallic ChemistryMCOR'RelectrophilicCM (B)CM (A)MLLLLLMLLLLL dyzdxzdxy C Cd (hy)Fischer (A)(B)

9 Zyx 3 Fischer Organometallic ChemistryMCOOCCOOCCOCO[M(CO)6] M = Cr, WRLiMCOCCOOCCOCOOLiRMe3 OBF4 MCOCCOOCCOCOOMeRM=C: (M = Cr, R = Ph)EtNH2 MCOCCOOCCOCONHEtR+ MeOH1)PhLi, -78 C2)HCL, -78 CWCOCCOOCCOCOPhPhM = WR = Ph1) BuLi2)BrCH2CO2 MeCrCOCCOOCCOCOOMeCH2CH2CO2 MeM = Cr, R = Me3 Fischer Organometallic ChemistryMOCCOOCCOCOCROR'M = Cr, Mo, WBX3(BCl3 etc) MXCOOCCOCOCRM = Cr, R = Me, X = I ( )M = Mo, R = Ph, X = Br(1973 Fischer) (carbyne complex)MCABsp22e donorMCAsp3e donor 3 Fischer Organometallic ChemistryMCRR'nucleophilicCM (B')CM (A')MLLLLLMLLLLLCCd (hy)dyzdxzdxy (A')(B')zyxSchrock -2 3 Schrock Organometallic ChemistryTatB uH2 CtB uH2 CClClCH2tBuTa(V)

10 Ta, Nb LiCH2-tBuTatB uH2 CtB uH2 CClCHtBuCH2tBu-CMe4 TatB uH2 CtB uH2 CButH2 CCtBuHTatB uH2 CtB uH2 CClCtBuHLiCH2-tBu-LiClHTaCtB uH2 CPMe3 CtBuH2 PMe3 PMe3tBuH 3 Schrock Organometallic ChemistryTaCH3CH3 ClClCH3 CpTlTaCH3CH3CH3Ph3 CBF4Ph3P=CH2 TaCH3CH2Ta(V)BrSiMe3 TaCH3CH2 SiMe3Br TaClCtBuHClTaClCHHClTaCHtBuH2 CCH2 (olefine methathesis)ethyleneCpTlL = CH2tBuCpTl3 Schrock Organometallic ChemistryTaCH2tBuCtBuHCl2 PMe3 -CMe4 TaPMe3 CtBuClPMe3 (alkylidyne complex MCABsp2-II anion, 4e donorMCAsp-III anion, 6e donor WCl6 LiCH2tButB uH2 CWtB uH2 CCtB uH2 CtBu2 PMe3 PMe3 WtB uH2 CCPMe3tBuCtBuHMCHMCMeMCtBu 3 Schrock Organometallic Chemistry MCQR'RMCRHQR' = OR, NHR (carbene complex) (alkylidene complex)R, R' = R, HFischer (1964)Schrock (1970)MCABsp2neutral, 2e donor (carbyne complex)MCAspneutral,3e donor MCR MCR (alkylidyne complex))