12 Oct. 2011

Laboratory for Coordination Chemistry

Masumi Itazaki (Lecturer)


1. Current Research and Principal Research Interests

My research topic is of transformation of molecules by transition metal complexes. I have been engaged especially in the area of organometallic chemistry including syntheses of mono- and multinuclear complexes and organic syntheses using organosilicon compounds. Several examples are shown as follows.

(1) Iron Complex Catalyst Which Introduces a Cyano Group of Acetonitrile into Carbonyl Compounds1,2
C-C bond cleavage of MeCN has been performed in the reaction with Et3SiH under the photolysis to give Et3SiCN catalyzed by Cp(CO)2FeMe. Addition of aldehydes or ketones to the reaction system has afforded the corresponding cyanohydrin silyl ether, where silylcyanation takes place. The iron complex derived from Cp(CO)2FeMe serves as a catalyst which introduces a CN group of MeCN into carbonyl compounds.

(2) Synthesis of New Type Trinuclear Hydridoplatinum Complexes with Bridging Phosphido Ligands and Its reactivity8
New di- and trinuclear phosphido-bridged platinum complexes with hydrido ligands have been prepared and mechanistic consideration has been done. Pt(PEt3)3 reacts with equimolar Ph2PH to afford the dinuclear complex 1 and the cyclic trinuclear complex 2 depending on the reaction conditions. Isolated complexes 1 and 2 cleanly react with Ph2PH to form 3. The hydrido ligand in 2 is readily replaced for a silyl group in the reaction with HSiR3. On the other hand, cationic triangular species [Pt3(μ-PPh2)3(PEt3)3]+ are obtained from the reaction of 2 with MeI and that with weak acid ArB(OH)2.


2. Selected Publications

1. “Iron-catalyzed Silylcyanation of Aldehydes and Ketones with Silyl Cyanide Prepared from Silane and Acetonitrile”, M. Itazaki and H. Nakazawa, Chem. Lett., 37, 1054-1055 (2005).

2. “Catalytic C-C Bond Cleavage and C-Si Bond Formation in Reaction of RCN with Et3SiH Promoted by an Iron Complex”, H. Nakazawa, K. Kamata, and M. Itazaki, Chem. Commun., 4004-4006 (2005).

3. “Ring-opening Isomerization of Methylenecyclopropanes Catalyzed by Hydridorhodium(I) Complexes”, M. Itazaki, Y. Nishihara, H. Takimoto, K. Osakada, J. Mol. Catal. A Chem., 241, 65-71 (2005).

4. “Hexanuclear Pt Complexes Composed of Two Cyclic Triplatinum Units Connected with 1,4-Diphenylene and 1,1'-Ferrocenylene Spacer”, M. Itazaki, O. Kitami, M. Tanabe, Y. Nishihara, K. Osakada, J. Organomet. Chem., 690, 3957-3962 (2005).

5. “Preparation of Pd(PPh2H)2(PPh3)2 and its Role as a Precursor of a Dinuclear Complex with Bridging Phosphide Ligands”, M. Itazaki, Y. Nishihara, K. Osakada, Transit. Met. Chem., 30, 828-830 (2005).

6. “Dinuclear Pt(II) and Pd(I) Complexes with Bridging PPh2 Ligands from the Reaction of PPh2H with Zero-valent Complexes of These Metals”, M. Tanabe, M. Itazaki, O. Kitami, Y. Nishihara, K. Osakada, Bull. Chem. Soc. Jpn., 78, 1288-1290 (2005).

7. “Selective C-C Bond Activation of 2-Aryl-1-methylenecyclopropanes Promoted by Ir(I) and Rh(I) Hydrido Complexes. Mechanism of Ring-opening Isomerization of the Strained Molecules”, Y. Nishihara, C. Yoda, M. Itazaki, K. Osakada, Bull. Chem. Soc. Jpn., 78, 1469-1480 (2005).

8. “[Pt2H2(μ-PR2)2(PEt3)2] (R = tBu, Ph) and [Pt3H2(μ-PPh2)4(PEt3)2]. Characterization of the Triangular Intermediate [Pt3H(μ-PPh2)3(PEt3)3] and Its Chemical Properties”, M. Itazaki, Y. Nishihara, K. Osakada, Organometallics, 23, 1610-1621 (2004).

9. “C-C and C-H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η1:η2-CH2CR2CH=CH2)(CO) (PPh3)2 and trans-M(CH=CHCMeR2)(CO)(PPh3)2 (M = Rh, Ir, R = CH2CH2Ph)”, M. Itazaki, C. Yoda, Y. Nishihara, K. Osakada, Organometallics, 23, 5402-5409 (2004).

10. “Platinum Complex Catalyzed Hydrosilylation and Isomerization of Methylene cyclopropane Derivatives. Effect of Structures of the Substrate and Catalyst”, M. Itazaki, Y. Nishihara, K. Osakada, J. Org. Chem., 67, 6889-6895 (2002).