Sungil Cho

Synthesis, X-ray crystal structure, and reactivity of the monomeric dithio-o-carboranyl iridium complex [Ir(η5-C5Me5)(η2-S2C2B10H10)]

Abstract The reaction between the pentamethylcyclopentadienyl complex [Cp*IrCl 2 ] 2 and the dilithium dithio- o -carborane salt, Li 2 [S 2 C 2 B 10 H 10 ] ( 1 ), in THF affords the o -carborane-substituted compound Cp*Ir(S 2 C 2 B 10 H 10 ) ( 2 ) in good yield. The complex [Cp*Ir(S 2 C 2 B 10 H 10 )] ( 2 ) has been isolated and characterized by X-ray diffraction analysis which confirmed a coordinatively unsaturated mononuclear complex. Subsequent addition reactions of complex 2 with the nucleophiles PMe 3 , CNBu t , and CO yield the corresponding complexes [Cp*Ir(S 2 C 2 B 10 H 10 )(PMe 3 )] ( 3 ), [Cp*Ir(S 2 C 2 B 10 H 10 )(CNBu t )] ( 4 ), and [Cp*Ir(S 2 C 2 B 10 H 10 )(CO)] ( 5 ). All of these new compounds have been isolated in high yield and characterized by IR and NMR spectroscopy. The solid state structures of 3 and 5 were determined by single-crystal X-ray diffraction analysis, exhibiting a characteristic three-legged ‘piano-stool’ arrangement around the iridium metal center.

Iron(II)–nitrile complexes: synthesis, structure and property of trans-[FeH(NCR)(dppe)2]+X− (dppe=Ph2PCH2CH2PPh2: R=CH3, CH2CH2OCH3, CH2CH2CH2Cl, C6H5: X=Cl, BPh4, BF4)

Abstract Dissolution of trans -FeHCl(dppe) 2 , 1 , in various nitriles under argon led to the formation of complexes of the type trans -[FeH(NCR)(dppe) 2 ]Cl ( 2a (R=CH 3 ), 3a (R=CH 2 CH 2 OMe), 4a (R=CH 2 CH 2 CH 2 Cl), 5a (R=Ph)) in several hours. Complexes 2a – 4a could be further converted to trans -[FeH(NCR)(dppe) 2 ][BPh 4 ] ( 2b – 4b ) and trans -[FeH(NCR)(dppe) 2 ][BF 4 ] ( 2c – 4c ) when they were treated with NaBPh 4 and NaBF 4 , respectively. The stability and electrochemical properties of these complexes appeared to depend mainly on their counteranions (Cl − , BPh 4 − , BF 4 − ). Compounds 2b , 2c , 3b , 3c , 4b and 4c reacted with KCN or NaCN to give [FeH(CN)(dppe) 2 ] ( 6 ). Compound 6 underwent electrophilic addition at the cyano nitrogen by RSO 3 CF 3 (R=Me, H) to give [FeH(CNR)(dppe) 2 ][SO 3 CF 3 ] ( 7a for R=Me, 7b for R=H). Crystallographic data for 2b : monoclinic space group P 2 1 / c , a =22.508(1) A, b =16.120(1) A, c =19.257(1) A, β =113.86(1)°, Z =4, R ( wR 2 )=0.0361(0.0882). Crystallographic data for 3b : triclinic space group P 1 , a =13.240(1) A, b =14.732(2) A, c =19.807(1) A, α =75.276(6)°, β =72.466(6)°, γ =82.033(6)°, Z =2, R ( wR 2 )=0.0368(0.0835). Crystallographic data for 7a : monoclinic space group P 2 1 / c , a =12.456(1) A, b =21.880(3) A, c =19.924(3) A, β =108.08(1)°, Z =4, R ( wR 2 )=0.0663 (0.1647).