TY - JOUR
T1 - Two coordination modes of TCNE in the ruthenium amidinates
T2 - The first example providing experimental evidence for κ1-N to η2-C rearrangement
AU - Kondo, Hideo
AU - Sue, Takashi
AU - Kageyama, Akira
AU - Yamaguchi, Yoshitaka
AU - Sunada, Yusuke
AU - Nagashima, Hideo
N1 - Funding Information:
This work was supported by Grant-in-Aid for Science Research on Priority Areas (No. 18064014, Synergy of Elements) from Ministry of Education, Culture, Sports, Science and Technology, Japan.
PY - 2009/3/1
Y1 - 2009/3/1
N2 - Reactions of Cp*Ru(κ2-N(R){double bond, long}C(R′)NR) (1a; R = iPr, R′ = Me, 1b; R = tBu, R′ = Ph) with TCNE initially give dark green colored intermediary species, which are readily converted to brown colored "η2-C" coordination complexes, Cp*Ru(κ2-N(R){double bond, long}C(R′)NR)(η2-TCNE) (3a; R = iPr, R′ = Me, 3b; R = tBu, R′ = Ph). These "η2-C" complexes are characterized by spectroscopy and crystallography. A stable ruthenium amidinate having a "κ1-N"-coordinated TCNE, Cp*Ru(κ2-N(tBu){double bond, long}C(Mes)NtBu)(κ1(N)-TCNE) (2c), is synthesized by treatment of Cp*Ru(κ2-N(tBu){double bond, long}C(Mes)NtBu) (1c) with TCNE, the structure of which is unequivocally confirmed by X-ray structure determination and the charge transfer nature is supported by ESR analysis. Close analogy in IR and UV-Vis spectroscopy of 2c with the dark green colored intermediary species formed from 1b suggests that this is "κ1-N" ruthenium amidinate, which is rearranged to the "η2-C" complex 3b.
AB - Reactions of Cp*Ru(κ2-N(R){double bond, long}C(R′)NR) (1a; R = iPr, R′ = Me, 1b; R = tBu, R′ = Ph) with TCNE initially give dark green colored intermediary species, which are readily converted to brown colored "η2-C" coordination complexes, Cp*Ru(κ2-N(R){double bond, long}C(R′)NR)(η2-TCNE) (3a; R = iPr, R′ = Me, 3b; R = tBu, R′ = Ph). These "η2-C" complexes are characterized by spectroscopy and crystallography. A stable ruthenium amidinate having a "κ1-N"-coordinated TCNE, Cp*Ru(κ2-N(tBu){double bond, long}C(Mes)NtBu)(κ1(N)-TCNE) (2c), is synthesized by treatment of Cp*Ru(κ2-N(tBu){double bond, long}C(Mes)NtBu) (1c) with TCNE, the structure of which is unequivocally confirmed by X-ray structure determination and the charge transfer nature is supported by ESR analysis. Close analogy in IR and UV-Vis spectroscopy of 2c with the dark green colored intermediary species formed from 1b suggests that this is "κ1-N" ruthenium amidinate, which is rearranged to the "η2-C" complex 3b.
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U2 - 10.1016/j.jorganchem.2008.12.030
DO - 10.1016/j.jorganchem.2008.12.030
M3 - Short survey
AN - SCOPUS:59849103914
SN - 0022-328X
VL - 694
SP - 795
EP - 800
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 5
ER -