TY - JOUR
T1 - Medium size macrocycles incorporating combinations of coordinated-1,3-diyne units, oxygen donors and group 14 elements
AU - Atkinson, Robert C.J.
AU - Hope-Weeks, Louisa J.
AU - Mays, Martin J.
AU - Solan, Gregory A.
N1 - Funding Information:
We acknowledge the financial support of the EPSRC (L.J.H.-W) and Dstl. Fort Halstead (L.J.H.-W). The help of the EPSRC mass spectrometry service, Swansea is gratefully acknowledged. Dr. John E. Davies is thanked for crystal structure determinations.
PY - 2007/4/15
Y1 - 2007/4/15
N2 - Two approaches have been employed to prepare medium size macrocycles incorporating combinations of coordinated-1,3-diyne units, oxygen donors and group 14 elements. In the first approach, the acid-catalysed reaction of [{Co2(CO)6(μ-η2-HOCH2C{triple bond, long}C{single bond})}2] (1a) with either C6H5OH, C6H4-1,4-(OH)2 or C6H4-1,2-(OH)2 was found to form in good to moderate yield the nine-membered [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2OC6H4}2] (2) and the eight-membered macrocycles, [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2-2,3-C6H2-1,4-(OH)2}] (3) and [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2-3,4-C6H2-1,2-(OH)2}] (4), respectively. In contrast, treatment of the bis-lithiated derivative of 1a with Cl2SiR1R2 affords the silicon-containing nine-membered macrocycles [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-OCH2C2C2CH2OSiR1R2}] (5a R1 = R2 = Me; 5b R1 = R2 = Ph; 5c R1 = Me, R2 = Ph). Similarly, the germanium analogue of 5b, [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-OCH2C2C2CH2OGePh2}] (6) can be prepared from Cl2GePh2. Single crystal X-ray diffraction studies have been reported on 2, 3, 5a, 5b and 6.
AB - Two approaches have been employed to prepare medium size macrocycles incorporating combinations of coordinated-1,3-diyne units, oxygen donors and group 14 elements. In the first approach, the acid-catalysed reaction of [{Co2(CO)6(μ-η2-HOCH2C{triple bond, long}C{single bond})}2] (1a) with either C6H5OH, C6H4-1,4-(OH)2 or C6H4-1,2-(OH)2 was found to form in good to moderate yield the nine-membered [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2OC6H4}2] (2) and the eight-membered macrocycles, [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2-2,3-C6H2-1,4-(OH)2}] (3) and [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2-3,4-C6H2-1,2-(OH)2}] (4), respectively. In contrast, treatment of the bis-lithiated derivative of 1a with Cl2SiR1R2 affords the silicon-containing nine-membered macrocycles [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-OCH2C2C2CH2OSiR1R2}] (5a R1 = R2 = Me; 5b R1 = R2 = Ph; 5c R1 = Me, R2 = Ph). Similarly, the germanium analogue of 5b, [{Co2(CO)6}2{cyclo-μ-η2:μ-η2-OCH2C2C2CH2OGePh2}] (6) can be prepared from Cl2GePh2. Single crystal X-ray diffraction studies have been reported on 2, 3, 5a, 5b and 6.
KW - Cobalt
KW - Coordinated 1,3-diyne
KW - Group 14
KW - Macrocycle
KW - Oxygen donor
UR - http://www.scopus.com/inward/record.url?scp=33947592845&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2007.01.026
DO - 10.1016/j.jorganchem.2007.01.026
M3 - Article
AN - SCOPUS:33947592845
VL - 692
SP - 2076
EP - 2085
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 10
ER -