Organometallic Chemistry in Supercritical Water: metallorganic Products of the CpCo-catalyzed Cyclotrimerization of Acetylenes
Cyclotrimerization of t-butylacetylene or phenylacetylene with cpCo(CO)2 as catalyst in supercritical water yields the isomeric 1.3.5-tris-substituted- (1: R=Ph. 1a: R=bu') and 1.2.4-tris-substituted benzene derivatives (2: R=Ph. 2a: R=bu'). The identification of the organometallic products obtained under these conditions is described. The formation of all possible isomers of the correspondig CpCo(bis-substituted-cyclobutadiene) (3,4). CpCo(vis-substituted-CpCobaltacyclopentadiene) (5.6.7) and CpCp(bis-substituted-cyclopentadienone) (8.9.10) via GC-MS is reported. Two of three isomers of CpCo(bis-substituted-cyclopentadienone) (8.9(R=Ph), 8a.9a (R=bu') were separated and characterized in substance. The structures of 8.9.8a and 9a were elucidated by single crystal X-ray diffraction. *crystallizes in the orthorhombic space group p222 (No.19) with a=840.5(1). B=1105.9(2). C=1767.2(3) pm. V=1642.8(1)x10 (6) pm (3), Z=4. Dcalc=1.441 g cm -3. R1=0.0501 (I>3) wR1=0.0529 (I>3). 9crystallizes in the orthorhombic space group pna2 (No.33) with a=1086.7(1). B=4726.0(1). C=1668.5(1) pm. V=8427.3(1)x10(6) pm(3),Z=20,Dcalc=1.404 g cm(-3). R=0.0705 (I>2). Rw=0.1321 (all data on F2). 8acrystallizes in the monoclinic space group P2 c(No. 14) with a=1441.63(3). B=1241.3(1). C=3672.66 pm. B=92.39(2) V=6566(2)x10(6) pm(3). Z=16. Dcalc=1.280 g cm(-3).R=0.082(I>2), Rw=0.144 (all data on F2). 9a crystallizes in the monoclinic space group P2 c (No 14) with a=669.3(1).c=1843.1(1)pm B=94.78(1) V1641.9(1)x10 pm Z=4.Dcalc=1.28 g cm-3, R=0.0622(I>2).Rw=0.1185 (all data on F2).
Bibliographic Reference: Article: Journal of Organometallic Chemistry, 570(1998), 121-127
Record Number: 199910601 / Last updated on: 1999-04-01
Original language: en
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