(5,10,15,20-Tetraphenylporphyrinato-κ⁴ N)(2,2,2-trifluoro-1-phenylethylidene-κC ¹)ruthenium(II): a stable fluorinated alkylidene complex of a ruthenium(II) porphyrin

Abstract

Key indicators: single-crystal X-ray study; T = 296 K; mean (C-C) = 0.004 Å; R factor = 0.031; wR factor = 0.078; data-to-parameter ratio = 16.5.In the title compound, [Ru(C 44 H 28 N 4 )(C 8 H 5 F 3 )], the fluorinated alkylidene group is bound to a five-coordinate Ru atom, which is located toward the carbene C atom, 0.3301 (5)Å from the least-squares plane of the C 20 N 4 porphyrin core. The Ru C bond is tilted slightly from the normal to the C 20 N 4 least-squares plane due to steric repulsion between the porphyrinate ligand and the bulky trifluoromethyl group. The Ru C bond length of 1.838 (2) Å is comparable with those in bis(subsituted phenyl)carbene analogs. Related literature Data collectionRigaku AFC-7R diffractometer Absorption correction: none 9374 measured reflections 8916 independent reflections 7578 reflections with I > 2(I) R int = 0.017 3 standard reflections every 150 reflections intensity decay: 3.5%

Gold(I) α‐Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies

“…Strikingly, despite the great interest and potential of gold carbene complexes, [15,16] we found only two isolated examples involving an α-CF 3 species, namely the CÀ H functionalization of phenothiazine/carbazole with PhC(=N 2 )CF 3 catalyzed by (phosphite)AuCl/AgSbF 6 . [17] In parallel to the synthetic developments, efforts have been made to prepare and characterize α-CF 3 carbene complexes, but only very few such species have been reported so far (Figure 2): the porphyrin Ru complex A, [18] the Fischer-type W complexes B [19] and the Schrock-type Ir, Co and Ni fluoro complexes C-E. [20] Of note, the Co and Ni carbene complexes D and E display reactivity relevant to the metathesis/polymerization of fluoro alkenes, but none of the isolated α-CF 3 carbene complexes was shown to undergo cyclopropanation or insertion reactions.…”

A Convergent, Modular Approach to Trifluoromethyl‐Bearing 5‐Membered Rings via Catalytic C(sp3)−H Activation

“…Attempts were made to directly observe the transient rhodium α‐CF 3 ‐α‐alkyl carbene intermediates generated in the reactions of various dirhodium(II) carboxylates with α‐CF 3 ‐α‐alkyl diazo compounds, but without success. We then turned our attention to the synthesis of ruthenium porphyrin α‐CF 3 ‐α‐alkyl carbene complexes, in view of the formation of desired C−H insertion product in the Ru( p ‐Cl‐TPP)CO‐catalyzed reaction (Figure 2A), and also considering that ruthenium porphyrin carbene complexes are relatively stable for isolation [14b,g, 27] . Treatment of Ru(TMP)CO with 75 and 76 (10 equiv) at 0 °C for 20 min led to the corresponding ruthenium carbene complexes 78 and 79 in 85 % and 65 % yield, respectively (Scheme 2A).…”

Gold(I) α‐Trifluoromethyl Carbenes: Synthesis, Characterization and Reactivity Studies

“…In parallel to the synthetic developments, efforts have been made to prepare and characterize α‐CF 3 carbene complexes, but only very few such species have been reported so far (Figure 2): the porphyrin Ru complex A , [18] the Fischer‐type W complexes B [19] and the Schrock‐type Ir, Co and Ni fluoro complexes C – E [20] . Of note, the Co and Ni carbene complexes D and E display reactivity relevant to the metathesis/polymerization of fluoro alkenes, but none of the isolated α‐CF 3 carbene complexes was shown to undergo cyclopropanation or insertion reactions.…”