TY - JOUR
T1 - Mono- and dinuclear high-spin half-sandwich manganese(II) complexes containing acetylide and TMEDA ligands
AU - Kheradmandan, Sohrab
AU - Fox, Thomas
AU - Schmalle, Helmut W.
AU - Venkatesan, Koushik
AU - Berke, Heinz
PY - 2004/9/6
Y1 - 2004/9/6
N2 - The d5 high-spin MnII half-sandwich complexes [Mn(C≡CR)(MeC5H4)(tmeda)] (R = SiMe3 2, Ph 3; tBu 4; C≡CSiMe3 5; C=CPh 6; tmeda = N,N,N′, N′-tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC5H4)2(tmeda)] (1) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C-C≡CSiMe3)2(tmeda)]2 (7) and [Mn2-(MeCp)2(μ1-tBuC≡C) 2(μ1-tmeda)] (8), which contain Mn-Mn bonds, were synthesized by treating 1 with an excess of HC≡C-C≡CSiMe3 or HC≡CtBu, respectively. Dinuclear complexes of the type [(MeC 5H4)(tmeda)MnC≡C-X-C≡CMn(tmeda)(C 5H4Me)] [X = 1,3-C6H4 9; 1,4-C 6H4 10; 4,4′-(C6H4) 2 11] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3-C6H4-(C≡CSnMe 3)2, 1,4-C6H4(C≡CSnMe 3)2 and 4,4′-(C6H4) 2-(C≡CSnMe3)2 in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono- and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X-ray diffraction studies have been performed on complexes 3 and 5-11.
AB - The d5 high-spin MnII half-sandwich complexes [Mn(C≡CR)(MeC5H4)(tmeda)] (R = SiMe3 2, Ph 3; tBu 4; C≡CSiMe3 5; C=CPh 6; tmeda = N,N,N′, N′-tetramethylethylenediamine) were prepared by the reaction of [Mn(MeC5H4)2(tmeda)] (1) with 1 equiv. of the corresponding acetylene or the trimethyltin acetylide. The dinuclear complexes [Mn(C≡C-C≡CSiMe3)2(tmeda)]2 (7) and [Mn2-(MeCp)2(μ1-tBuC≡C) 2(μ1-tmeda)] (8), which contain Mn-Mn bonds, were synthesized by treating 1 with an excess of HC≡C-C≡CSiMe3 or HC≡CtBu, respectively. Dinuclear complexes of the type [(MeC 5H4)(tmeda)MnC≡C-X-C≡CMn(tmeda)(C 5H4Me)] [X = 1,3-C6H4 9; 1,4-C 6H4 10; 4,4′-(C6H4) 2 11] were obtained by treatment of 1 with 0.5 equiv. of the corresponding acetylides 1,3-C6H4-(C≡CSnMe 3)2, 1,4-C6H4(C≡CSnMe 3)2 and 4,4′-(C6H4) 2-(C≡CSnMe3)2 in benzene for 24 h to yield the corresponding dinuclear complexes in very good yields. All the mono- and dinuclear compounds have been characterized by NMR, IR, Raman spectroscopy and elemental analyses. X-ray diffraction studies have been performed on complexes 3 and 5-11.
KW - Alkyne ligands
KW - Cyclopentadienyl ligands
KW - Half-sandwich complexes
KW - Molecular devices
KW - N ligands
UR - http://www.scopus.com/inward/record.url?scp=4944235124&partnerID=8YFLogxK
U2 - 10.1002/ejic.200400006
DO - 10.1002/ejic.200400006
M3 - Article
AN - SCOPUS:4944235124
SN - 1434-1948
SP - 3544
EP - 3554
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 17
ER -