3. , 3. , 3. , 3. Pph, and J. Hh-=, 93 (s, 4H, 22% yield). 1 H NMR (400 MHz ppm): 9.01 (d, 2H, 3 J HH = 4.8 Hz 3H, 3 J HH = 7.2 Hz, H fluorenyl, H 5 ), 7.97 (d, 2H, 3 J HH = 8.0 Hz, H phenylene ), 7.71 (m, 11H, H fluorenyl, H 8 and ortho H PPh ) meta H PPh ), 7.03 (m, 10H, 3 J HH ~ 7.6 Hz, meta H PPh and H phenylene ), 4.22 (s, 4H, 2CH 2-fluorenyl ), 4.21 (s, 2H, 1CH 2-fluorenyl ) ppm) : 50.0 (s). MS (ESI in CH 2 Cl 2 /CH 3 CN): calcd for C 119 H 89 ClN 4 P 4 Ru: 1835.4 [MH] + , found 1835, pp.41281779-128

M. Ms, Elemental Analysis: calcd for C 119 H 89 ClN 4 P 4 Ru : C, 77, 10 -3 M -1 .cm -1 ), CH 2 Cl 2 FT-IR (KBr disc, pp.263-423, 1835.

Z. Synthesis, trifluorenyl)-20-(4-ethynyl-ruthenium-phenyl) porphyrinato 4 -In a Schlenk tube, mmol) and [Ru(dppe, p.15

. Cl, The mixture was monitored by 31 P and 1 H NMR spectroscopy, and the reaction was complete in 72 hours. The solution was concentrated under reduced pressure and adding ether gave the desired vinylidene as the precipitated solid. The unreacted ruthenium salt remained in ether. The precipitate was filtered, dissolved in 10 mL of DCM and triethylamine (0.25 mL) was added dropwise to the solution. The brown green solution was then concentrated and passed through a short basic alumina column using DCM and 2% triethylamine as eluent. The solution was concentrated and addition of ether gave a greenish brown precipitate which was filtered and identified as 4. (19 mg, 25% yield). 1 H NMR (400 MHz, distilled dichloromethane (DCM, 20 mL) was stirred under argon 9.03 (s, 4H, H ?-pyrrolic ), 8.41 (m, 3H, H fluorenyl, H 1 ), 8.28 (m, 3H, H fluorenyl, pp.7-53

1. and J. Hh-~-7-ipso-pph, 6 Hz, meta H PPh and H phenylene ), 4.22 (s, 4H, 2CH 2-fluorenyl ), 4.21 (s, 2H, 1CH 2-fluorenyl ), 2.80 (m, 8H, HH ~ 7.6 Hzpara PPh), 129.0 (para PPh) ppm): 49.7 (s). MS (ESI in CH 2 Cl 2 /CH 3 CN): calcd for C 119 H 87 ClN 4 P 4 ZnRu: 1898.3923 [M] + , found: 1898.3932 [M] + . Elemental analysis: calcd References, pp.31-81

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