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Reversible protonation of the purple ruthenabenzofuran (or tethered ruthenacyclohexadiene) Ru[C 5 H 2 (CO 2 Me-2)(CO 2 Me-4)(CHCO 2 Me-5)](CO)(PPh 3 ) 2 ( 1 ) with HBF 4 ·OEt 2 gives the structurally characterized stable cationic tethered ruthenabenzene [Ru[C 5 H 2 (CO 2 Me-2)(CO 2 Me-4)(CH 2 CO 2 Me-5)](CO)(PPh 3 ) 2 ][(BF 4 ) 2 H] ( 2 ), while the thermal reaction of 1 with HCl forms the stable neutral tethered ruthenabenzene Ru[C 5 H 2 (CO 2 Me-2)(CO 2 Me-4)(CH 2 CO 2 Me-5)]Cl(PPh 3 ) 2 ( 3 ) as the major product. The cyclopentadienyl complex Ru(η 5 -C 5 H 2 (CH 2 CO 2 Me-1)(CO 2 Me-2)(CO 2 Me-4)Cl(CO)(PPh 3 ) ( 4 ), which is formed in this reaction as a minor product, can be separated from 3 by chromatography. Treatment of the ruthenabenzene 3 with CNR (R = p -tolyl) gives the purple ruthenabenzofuran (or tethered ruthenacyclohexadiene) complex Ru[C 5 H 2 (CO 2 Me-2)(CO 2 Me-4)(CHCO 2 Me-5)](CNR)(PPh 3 ) 2 ( 5 ), which is the isocyanide analogue of 1 .
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Clark et al. (2008) studied this question.
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