[
    {
        "id": "authors:vhk78-fqw48",
        "collection": "authors",
        "collection_id": "vhk78-fqw48",
        "cite_using_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180521-125717579",
        "type": "article",
        "title": "Synthesis, Structure, and Reactivity of a Rhenium Oxo-Vinylalkylidene Complex",
        "author": [
            {
                "family_name": "Flatt",
                "given_name": "Brenton T.",
                "clpid": "Flatt-B-T"
            },
            {
                "family_name": "Grubbs",
                "given_name": "Robert H.",
                "orcid": "0000-0002-0057-7817",
                "clpid": "Grubbs-R-H"
            },
            {
                "family_name": "Blanski",
                "given_name": "Rusty L.",
                "clpid": "Blanski-R-L"
            },
            {
                "family_name": "Calabrese",
                "given_name": "Joseph C.",
                "clpid": "Calabrese-J-C"
            },
            {
                "family_name": "Feldman",
                "given_name": "Jerald",
                "clpid": "Feldman-J"
            }
        ],
        "abstract": "The reaction of 3 equiv of KOC(CF_3)_2Me with ReOCl_3(PPh_3)_2 in dichloromethane, followed by recrystallization from hexanes/THF, gives ReO[OC(CF_3)_2Me]_3(THF)_2( 1) in 35 7% yield. An\nX-ray diffraction study of 1 (monoclinic, P2_1/n, a = 10.010(3) \u00c5, b = 29.247(6) \u00c5, c = 10.800(3) \u00c5, \u03b2 = 117.09(1)', Z = 4) reveals a facial arrangement of the three alkoxide ligands around the metal center in a distorted octahedron. The ligand environment in 1 is quite crowded, as evidenced by an elongated Re-O bond between rhenium and one of the THF ligands. The reaction of 3,3-diphenylcyclopropene with 1 in dichloromethane gives initially a mixture of two isomeric rhenium oxo-vinylalkylidene complexes, of which the isomer syn,mer-ReO[C(H)-CH=CPh_2] [OC(CF3)2Me]3(THF) (2b) was isolated in 87% yield. An X-ray diffraction study of 2b (triclinic, P1^(bar), a = 10.459(3) \u00c5, b = 10.913(3) \u00c5, c = 21.308(6) \u00c5, \u03b1 = 91.16(3)\u00b0,\u03b2 = 102.05-(2)\u00b0, \u03b3 = 117.98(2)\u00b0, 2 = 2) supports a pseudooctahedral structure with mutually trans vinylalkylidene and THF ligands. Complex 2b does not react readily with internal or terminal olefins; however, the addition of GaBr_3 (1 equiv) to 2b yields moderately active catalyst(s) that metathesize cis-2-pentene at ~6.7 turnovers min^(-1). No propagating alkylidene species are observed during the metathesis reaction.",
        "doi": "10.1021/om00019a032",
        "issn": "0276-7333",
        "publisher": "American Chemical Society",
        "publication": "Organometallics",
        "publication_date": "1994-07",
        "series_number": "7",
        "volume": "13",
        "issue": "7",
        "pages": "2728-2732"
    }
]