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• W1997532416 abstract "Abstract The synthesis of P ‐functionalized molybdenum chelate complexes incorporating the linked cycloheptatrienyl‐phosphane ligand [2‐(diisopropylphosphanyl)phenyl]cycloheptatrienyl ( o ‐ i Pr 2 P−C 6 H 4 −C 7 H 6 ) is described. From the ligand precursor [2‐(cyclohepta‐2,4,6‐trienyl)phenyl]diisopropylphosphane ( 1 ) the paramagnetic 17‐electron dibromide [( o ‐ i Pr 2 PC 6 H 4 ‐η 7 ‐C 7 H 6 )MoBr 2 ( P − Mo )] ( 2 ) can readily be obtained. This is a versatile starting material for the preparation of cycloheptatrienyl molybdenum hydrides [( o ‐ i Pr 2 PC 6 H 4 ‐η 7 ‐C 7 H 6 )Mo(η 2 ‐BH 4 )( P − Mo )] ( 3 ) and [( o ‐ i Pr 2 PC 6 H 4 ‐η 7 ‐C 7 H 6 )Mo(PPh 3 )H( P − Mo )] ( 4 ). Treatment of 3 with dimethylanilinium tetraphenylborate ([PhNMe 2 H][BPh 4 ]) allows the production of the cationic 14‐electron complex fragment [( o ‐ i Pr 2 PC 6 H 4 ‐η 7 ‐C 7 H 6 )Mo( P − Mo )] + ( 13 ), which can be stabilized in the presence of suitable ligands L. The complexes [( o ‐ i Pr 2 PC 6 H 4 ‐η 7 ‐C 7 H 6 )MoL 2 ( P − Mo )]BPh 4 [L = dimethylphenyl isocyanide, ( 5 )BPh 4 ; L 2 = η 4 ‐2,5‐norbornadiene, ( 6 )BPh 4 ; L 2 = η 2 ‐phenylacetylene, ( 7 )BPh 4 ; L 2 = η 2 ‐ tert‐ butylacetylene, ( 8 )BPh 4 ] can thus be isolated in good yields. The alkyne complex ( 7 )BPh 4 can be used as a single‐source catalyst for the oligomerization of phenylacetylene, affording a mixture of triphenylbenzenes and linear oligomers. Quantum chemical calculations reveal an intimate relationship between the catalytically active 14‐electron complex fragment [( o ‐ i Pr 2 PC 6 H 4 ‐η 7 ‐C 7 H 6 )Mo( P − Mo )] + ( 13 ) and hypothetical isoelectronic and isolobal complexes of the type [( o ‐ i Pr 2 PC 6 H 4 ‐η 5 ‐C 5 H 4 )M( P − M )] + (M = Ru, 14 ; M = Os, 15 ), indicating that cycloheptatrienyl molybdenum systems might in general be a suitable replacement for cyclopentadienyl ruthenium and osmium catalysts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)" @default.
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• W1997532416 date "2003-03-01" @default.
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• W1997532416 title "Chelate Complexes of Functionalized Cycloheptatrienyl Ligands: Molybdenum Complexes with Linked Cycloheptatrienyl‐Phosphane Ligands and Their Use in Catalytic Carbon−Carbon Bond Formation" @default.
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• W1997532416 doi "https://doi.org/10.1002/ejic.200390140" @default.
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