TY - JOUR
T1 - Reactions of α,ω-dithiolate ligands with bis(cyclopentadienyl) molybdenum dichloride; Crystal structures of Mo(η-C5H 5)2{S(CH2)nS)} (n = 2, 3) and a layered hydrate, Mo(η-C5H5)2(SCH 2CH2O)·4.5H2O
AU - Lindsell, W. Edward
AU - Rosair, Georgina M.
AU - Rothmann, Michael M.
PY - 2005/1/3
Y1 - 2005/1/3
N2 - Reaction of bis(cyclopentadienyl)molybdenum dichloride 1 in ethanol with 1,3-propanedithiol 2 either in the presence of base or as its thallium derivative produces [Mo(?-C5H5)2(SCH 2CH2 CH2S)] (5) containing a 6-membered ring with a chair conformation, structurally characterized by X-ray diffraction. However, reactions of compound 1 with 2,2'-thiodiethanethiol (3) or 2,2'-oxydiethanethiol (4) under the same conditions do not form complexes with 8-membered chelate rings but lead to thioether or ether bond cleavage, respectively, to yield as major products [Mo(?-C5H 5)2(SCH2CH2X)] (6, X = S, or 7, X = O), containing ligands which form 5-membered rings; crystal structures of 6 and 7 are reported and both contain chelating ligands with envelope conformations. Compound 7 readily incorporates water and the unusual crystal structure of the hydrate Mo(?-C5H5)2(SCH2 CH 2O)·4.5H2O comprises stacks of double layers of hydrated organometallic molecules of overall composition [{Mo(?-C 5H5)2(SCH2CH2O)} 2 • H2O]n separated by layers of hydrogen-bonded water molecules, interconnected by H-bonds between H 2O molecules and O-atoms of the 2-thioethoxy ligand. © 2004 Elsevier B.V. All rights reserved.
AB - Reaction of bis(cyclopentadienyl)molybdenum dichloride 1 in ethanol with 1,3-propanedithiol 2 either in the presence of base or as its thallium derivative produces [Mo(?-C5H5)2(SCH 2CH2 CH2S)] (5) containing a 6-membered ring with a chair conformation, structurally characterized by X-ray diffraction. However, reactions of compound 1 with 2,2'-thiodiethanethiol (3) or 2,2'-oxydiethanethiol (4) under the same conditions do not form complexes with 8-membered chelate rings but lead to thioether or ether bond cleavage, respectively, to yield as major products [Mo(?-C5H 5)2(SCH2CH2X)] (6, X = S, or 7, X = O), containing ligands which form 5-membered rings; crystal structures of 6 and 7 are reported and both contain chelating ligands with envelope conformations. Compound 7 readily incorporates water and the unusual crystal structure of the hydrate Mo(?-C5H5)2(SCH2 CH 2O)·4.5H2O comprises stacks of double layers of hydrated organometallic molecules of overall composition [{Mo(?-C 5H5)2(SCH2CH2O)} 2 • H2O]n separated by layers of hydrogen-bonded water molecules, interconnected by H-bonds between H 2O molecules and O-atoms of the 2-thioethoxy ligand. © 2004 Elsevier B.V. All rights reserved.
KW - Cyclopentadienyl
KW - Hydration
KW - Layer structure
KW - Molybdenum
KW - Thiolate
UR - http://www.scopus.com/inward/record.url?scp=11044237291&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2004.08.040
DO - 10.1016/j.jorganchem.2004.08.040
M3 - Article
SN - 0022-328X
VL - 690
SP - 126
EP - 133
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -