REACTIVITY PATTERNS FOR MULTISITE-BOUND ACETYLIDES - NUCLEOPHILIC-ATTACK AT THE ALPHA-CARBON IN MU-2-ETA-2-ACETYLIDES - BRIDGING 2-AMINO-1-METALLAPHENETHYLIDENE COMPLEXES VIA ADDITION OF PRIMARY AMINES TO FE2(CO)6(MU-2-ETA-2-C=CPH)(MU-PPH2), RU2(CO)6(MU-2-ETA-2-C=CPH)(MU-PPH2, OS2(CO)6(MU-2-ETA-2-C=CPH(MU-PPH2)

被引：31

作者：

CHERKAS, AA ^{[1
]}

RANDALL, LH ^{[1
]}

TAYLOR, NJ ^{[1
]}

MOTT, GN ^{[1
]}

YULE, JE ^{[1
]}

GUINAMANT, JL ^{[1
]}

CARTY, AJ ^{[1
]}

机构：

[1] UNIV WATERLOO,GUELPH WATERLOO CTR GRAD WORK CHEM,DEPT CHEM,WATERLOO CAMPUS,WATERLOO N2L 3G1,ONTARIO,CANADA

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 05期

关键词：

D O I：

10.1021/om00119a046

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The binuclear σ-π-acetylides M2(CO)6(µ2-η2-C≡CPh)(µ-PPh2) (1a, M = Fe; lb, M = Ru; 1c, M = Os) react with cyclohexylamine to form the two-carbon-bridged iminium complexes M2(CO)6[µ2-C{NHR}CH-(Ph)](μ-PPh2) (3a‒c, R = c-C6H11) in all three cases by attack at the α-carbon of the acetylide of 1 and proton transfer across the acetylide triple bond. The new ligands in 3a‒c are 2-(cyclohexylamino)-1-metallaphenethylidene derivatives with a carbene-like carbon atom coordinated to one metal and an sp3 carbon atom, derived from Cβ of the acetylide attached to the second metal. Analogous complexes M2(CO)6[µ2-C{NH(i-Pr)}CH(Ph)](µ-PPh2) (M = Ru, 5b; M = Os, 5c) have been characterized from the reactions of 1b and 1c with isopropylamine. Complex 1a only also forms the product of β-acetylide addition M2(CO)6[µ2-CHC(NRH)Ph](µ-PPh2). The entire triad of two-carbon-bridged products from 1a‒c with cyclohexylamine, M2(CO)6[µ2-C{NH(Cy)}CH(Ph)](µ-PPh2) (3a‒c), have been characterized by IR and1H,13C{1H}, and31P{1H} NMR spectroscopy and by single-crystal X-ray diffraction. Crystals of 3b,c are monoclinic space group P21/c with the following unit cell dimensions: 3b, a = 10.076 (3), b = 17.290 (4), c = 20.807 (4) Å, β = 102.18 (2)°, Z = 4; 3c, a = 10.164 (2), b = 17.126 (5), c = 20.691 (5) Å, β = 99.44 (2)°, Z = 4. The two structures were solved by the heavy-atom method and refined to the following R and Rw values: 3b, R = 0.030, Rw = 0.035 on 4372 observed diffractometer data; 3c, R = 0.035, Rw = 0.038 on 4051 observed data. Comparison with the structure of 3a determined earlier shows that all three molecules are isostructural, with M‒M bond lengths of 2.628 (1) Å for 3a, 2.7896 (4) Å for 3b, and 2.8197 (5) Å for 3c. Changes in the metal‒hydrocarbyl interactions down the triad are discussed. © 1990, American Chemical Society. All rights reserved.

引用

页码：1677 / 1685

页数：9

共 50 条

[1] CARBON-CARBON BOND FORMATION ON MULTISITE-BOUND UNSATURATED LIGANDS - SYNTHESIS OF MU-2-ETA-2-ALLENYL COMPLEXES VIA CARBENE ADDITION TO THE BINUCLEAR ACETYLIDES RU2(CO)6(MU-2-ETA-2-C=CR)(MU-PPH2)
NUCCIARONE, D
TAYLOR, NJ
CARTY, AJ
[J]. ORGANOMETALLICS, 1986, 5 (06) : 1179 - 1187
[2] POLYNUCLEAR ACETYLIDES - SYNTHESIS, SPECTROSCOPIC FEATURES, AND STRUCTURAL SYSTEMATICS FOR A COMPLETE TRIAD OF MU-2-ETA-2-COMPLEXES - M2(CO)6(MU-2-ETA-2-C=CR)(MU-PPH2)(M=FE,RU,OS)
CHERKAS, AA
RANDALL, LH
MACLAUGHLIN, SA
MOTT, GN
TAYLOR, NJ
CARTY, AJ
[J]. ORGANOMETALLICS, 1988, 7 (04) : 969 - 977
[3] ELECTRON RICH ACETYLIDE CLUSTERS - MOLECULAR AND ELECTRONIC-STRUCTURE AND REACTIONS OF OS3(CO)7(MU-2-ETA-2-C=CPH, OS3(CO)7(MU-2-ETA-2-C=CPRI)2(MU-PPH2)2)2(MU-PPH2)2 - 50-ELECTRON SPECIES WITH EXPANDED METAL FRAMEWORKS
CHERKAS, AA
TAYLOR, NJ
CARTY, AJ
[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1990, (05) : 385 - 387
[4] A TRIAD OF ELECTRON-RICH MU2-ALKYLIDENE COMPLEXES M2(CO)6[MU-CHC(PH)NET2](MU-PPH2)(M=FE,RU,OS) VIA THE ADDITION OF DIETHYLAMINE TO THE ACETYLIDES M2(CO)6(MU2-ETA-2-C=CPH)(MU-PPH2) - SPECTROSCOPIC PROPERTIES AND STRUCTURAL CHEMISTRY
CHERKAS, AA
MOTT, GN
GRANBY, R
MACLAUGHLIN, SA
YULE, JE
TAYLOR, NJ
CARTY, AJ
[J]. ORGANOMETALLICS, 1988, 7 (05) : 1115 - 1121
[5] Diiron acetylide complexes: Molecular structures of [Fe2(CO)4(mu-C CPh)(mu-PPh2)(mu-dppm)] and [Fe-2(CO)(3)(Ph2PC CPh)(mu-C CPh)(mu-PPh2)(mu-dppm)]
Hogarth, G
Redmond, SP
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 534 (1-2) : 221 - 227
[6] HYDRODEMETALATION OF ALKYNES AND DIYNES - DIIRON COMPLEXES OF MU-ETA-1-ETA-2-ALKENYL LIGANDS WITH PENDANT ALKYNES - CRYSTAL AND MOLECULAR-STRUCTURE OF FE2(CO)6(MU-PPH2) (MU-2-ETA-1-ETA-2-CH = CH2) AND FE2(CO)6(MU-PPH2)(MU-2-ETA-1-ETA-2-C(C-EQUIVALENT-TO-CME) = CHME)
MACLAUGHLIN, SA
DOHERTY, S
TAYLOR, NJ
CARTY, AJ
[J]. ORGANOMETALLICS, 1992, 11 (12) : 4315 - 4325
[7] Comparative chemistry of mu-eta(1):eta(2)-allenyl and mu-eta(1):eta(2)-acetylide complexes: eta(5)-Cyclopentadienyl complexes via alkyne-allenyl coupling in the reactions of PhC CPh with [Ru-2(CO)(6){mu-eta(1):eta(2)(beta,gamma)-C(Ph)=C=CH2}(mu-PPh(2))] and [Ru-2(CO)(6){mu-eta(1):eta(2)-C CPh}(mu-PPh(2))]. X-Ray structures of [{Ru-2(CO)(4){mu-eta(2)(C,O),eta(5)-C(5)MePh(2)(C6H4)(O)}(mu-PPh2)}(2)] and [Ru-2(CO)(5){mu-eta(2)(C,O),eta(5)-C(5)HPh(2)(C6H4)(O)}(mu-PPh(2))]
Breckenridge, SM
Taylor, NJ
Carty, AJ
Pellinghelli, MA
Tiripicchio, A
Sappa, E
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 506 (1-2) : 229 - 240
[8] CONVERSION OF A MU-ETA-2-ACETYLIDE TO A MU-ETA-2-PARALLEL-TO-ACETYLENE VIA SUCCESSIVE NUCLEOPHILIC ADDITIONS - X-RAY STRUCTURE OF OS2(CO)6[MU-ETA-2-C(C(NH-TERT-BU)(S-N-BU))CPH](MU-PPH2)
CHERKAS, AA
CARTY, AJ
SAPPA, E
PELLINGHELLI, MA
TIRIPICCHIO, A
[J]. INORGANIC CHEMISTRY, 1987, 26 (19) : 3201 - 3204
[9] COORDINATED PHOSPHOLES FROM THE COUPLING OF ALKYNES WITH BRIDGING PHOSPHIDO LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURES OF [CO2(MU-ETA-2 ETA-2'-C4(CO2ME)4PPH2)-(MU-PPH2)(CO)4], [MN2(ETA-4-C4H4PPH2)(MU-PPH2)(CO)6], AND [MN2(MU-ETA-5-C4H4PPH2)(MU-PPH2)-(CO)5]
BRAGA, D
CAFFYN, AJM
JENNINGS, MC
MAYS, MJ
MANOJLOVICMUIR, L
RAITHBY, PR
SABATINO, P
WOULFE, KW
[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (18) : 1401 - 1403
[10] SYNTHESIS AND DERIVATIVE CHEMISTRY OF [RU2(MU-PPH2)(MU-OH)2(ETA-6-P-CYMENE)2]+
CABEZA, JA
MULLA, F
RIERA, V
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1994, 470 (1-2) : 173 - 177

← 1 2 3 4 5 →