2020
DOI: 10.3390/app10196665
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Pt(II) Derivatives with Rollover-Coordinated 6-substituted 2,2′-bipyridines: Ligands with Multiple Personalities

Abstract: We report here the synthesis, characterization and behavior of a series of Pt(II) cyclometalated rollover complexes with two substituted bipyridines, 6-ethyl-2,2′-bipyridine (bpy6Et) and 6-methoxy-2,2′-bipyridine (bpy6OMe), in comparison with previously studied 2,2′-bipyridine complexes. The two ligands have similar steric hindrance but different electronic properties. As a result, the reactivity of the two series of complexes follows very different routes. In particular, the new complexes behave differently t… Show more

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Cited by 4 publications
(3 citation statements)
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“…Due to the presence of uncoordinated nitrogen, the rollover complex 1b is able to follow reaction paths not available to 1a , such as N-coordination (synthesis of dinuclear homo- and hetero-dimetallic species) [ 12 ], protonation [ 11 ], and retro-rollover reactions [ 13 ] as shown in Scheme 1 . Furthermore, taking advantage of the uncoordinated nitrogen, complex 1b has found application in organic synthesis, through an oxidative-addition/reductive-elimination reaction sequence which seems to be not available for 1a , 2a , and 2b [ 17 ].…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Due to the presence of uncoordinated nitrogen, the rollover complex 1b is able to follow reaction paths not available to 1a , such as N-coordination (synthesis of dinuclear homo- and hetero-dimetallic species) [ 12 ], protonation [ 11 ], and retro-rollover reactions [ 13 ] as shown in Scheme 1 . Furthermore, taking advantage of the uncoordinated nitrogen, complex 1b has found application in organic synthesis, through an oxidative-addition/reductive-elimination reaction sequence which seems to be not available for 1a , 2a , and 2b [ 17 ].…”
Section: Resultsmentioning
confidence: 99%
“…The principal difference between classical and rollover complexes is the presence of the uncoordinated donor atom, usually a nitrogen. This presence extends the reactivity of the complex, leading to reactions not available for classical compounds, such as protonation [ 11 ] and coordination [ 12 ]. The acquisition of a hydrogen ion may allow a retro-rollover reaction [ 13 ], opening up new catalytic possibilities in the field of hydrogen transfer reactions ( Scheme 1 ) [ 9 , 14 ].…”
Section: Introductionmentioning
confidence: 99%
“…In order to shed light into the delicate balance between steric and electronic effects, Zucca and coworkers investigated the influence of substituents CH 3 , CF 3 , CH 2 CH 3 , and OCH 3 , [ 39 , 40 , 41 ], two couples of substituents having similar steric hindrance (CH 3 and CF 3 ; CH 2 CH 3 and OCH 3 ), but different electronic effects. For the first couple, the location of CH 3 and CF 3 in position 6 or 5 allows to separate, in part, electronic and steric influences ( Figure 11 ).…”
Section: C–h Bond Activation Through Rollover Cyclometalationmentioning
confidence: 99%