[506443-55-6] C44H59MoNO2 (MW 729.90) InChI = 1S/C24H34O2.C10H15N.C10H12.Mo/c1-13-11-17(23(5,6)7)... more [506443-55-6] C44H59MoNO2 (MW 729.90) InChI = 1S/C24H34O2.C10H15N.C10H12.Mo/c1-13-11-17(23(5,6)7)21(25)19(15(13)3)20-16(4)14(2)12-18(22(20)26)24(8,9)10;11-10-4-7-1-8(5-10)3-9(2-7)6-10;1-10(2,3)9-7-5-4-6-8-9;/h11-12,25-26H,1-10H3;7-9H,1-6H2;1,4-8H,2-3H3;/q;;;+2/p-2/t;7-,8+,9-,10-;;InChIKey = HCKDLEPUKVGKLH-PVFISKEKSA-LSolubility: soluble in diethyl ether, benzene, n-pentane, dichloromethane, and most organic solvents.Form SuSpplied in: light yellow powder.Purification: recrystallized under an inert atmosphere from n-pentane at −30 °C. The n-pentane is generally rendered ‘olefin-free’ by repeated stirring over sulfuric acid until the addition of acid no longer results in discoloration; it is subsequently washed with deionized water and a saturated aqueous solution of NaHCO3 followed by normal purification.Handling, Storage, and Precautions: air and moisture sensitive. The complex should be stored at, or below, −20 °C and under an inert atmosphere (N2 or Ar). Solvents should be distill...
Two diastereomers of the monoalkoxidepyrrolide (MAP) species, W(NAr)(CH(2))(Me(2)Pyr)(OR*) (1; Ar... more Two diastereomers of the monoalkoxidepyrrolide (MAP) species, W(NAr)(CH(2))(Me(2)Pyr)(OR*) (1; Ar = 2,6-diisopropylphenyl, Me(2)Pyr = 2,5-dimethylpyrrolide, OR* = (R)-3,3'-dibromo-2'-(tert-butyldimethylsilyloxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2-olate), were generated through addition of R*OH to W(NAr)(CH(2))(Me(2)Pyr)(2). The unsubstituted tungstacyclobutane species, W(NAr)(C(3)H(6))(Me(2)Pyr)(OR*) (2), was isolated by treating the mixture of diastereomers of 1 with ethylene. An X-ray study revealed 2 to have a trigonal bipyramidal structure in which the imido and phenoxide ligands are in axial positions. A variety of NMR experiments were carried out on 1 and 2. The major findings are the following: (i) the methylidene ligands in the two diastereomers of 1 rotate readily about the W horizontal lineC bond (k = 2-7 s(-1) at 22 degrees C); (ii) NMR studies are consistent with 2 breaking up to give an intermediate alkylidene/ethylene complex, (R)- and (S)-W(CH(2))(C(2)H(4)); and (iii) the ethylene in the (R)-W(CH(2))(C(2)H(4)) intermediate can rotate about the W-ethylene bond axis at approximately the same rate as 2 re-forms or ethylene is lost to give 1. Compound 1 reacts with trimethylphosphine to yield (R)-1(PMe(3)). Two intermediate PMe(3) adducts were observed and found to convert to (R)-1(PMe(3)) in an intramolecular fashion with an average rate constant at 5 degrees C of approximately 1.4 x 10(-4) s(-1). Both neophylidene (4) and methylidene (5) MAP species containing 2,3,5,6-tetraphenylphenoxide ligand also were prepared. Compound 5 can be heated to 80 degrees C, where methylidene rotation about the W=C bond is facile and observable in a variable-temperature (1)H NMR spectrum. A (1)H-(1)H EXSY spectrum of 5 in benzene-d(6) at 20 degrees C showed that the methylidene protons are exchanging with k = 90 s(-1). A structure of 5(THF) showed it to be a square pyramid with the methylidene ligand in the apical position and THF coordinated trans to the imido…
... Scheme 2) and 3; 4a was previously pre-pared by a two-step synthesis requiring 11 weeks.[291 ... more ... Scheme 2) and 3; 4a was previously pre-pared by a two-step synthesis requiring 11 weeks.[291 Phos-phaalkenes such as 4a are readily identified by their charac-teristic low-field 31P and I3C chemical shifts and diagnostic 'Jcp coupling", 21 ... 161 A. H. Cowley, AR Barron, Ace. ...
ABSTRACT Grafting [Mo(NAr)(CHCMe2R1)(NR2)(2)] on SiO2-(700) gives [(SiO)Mo(NAr)(CHCMe2R1)(NR2)] a... more ABSTRACT Grafting [Mo(NAr)(CHCMe2R1)(NR2)(2)] on SiO2-(700) gives [(SiO)Mo(NAr)(CHCMe2R1)(NR2)] as a major surface species along with [(SiO)Mo(NAr)(CH2CMe2R1)(NR2)(2)] according to mass balance analysis, IR and NMR spectroscopies. The replacement of one amido group by a siloxy group from the surface of silica dramatically increased the activity of the Mo complex in olefin metathesis, and tuning the imido ligands allows the reactivity to be increased by at least one order of magnitude so that an overall turnover of 231 000 can be achieved in the metathesis of propene. Additionally, ethyl oleate can also be converted into a thermodynamic equilibrated mixture in 8 h with only 0.02% of catalyst.
Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathe... more Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathesis (ARCM) with 2-5 mol % chiral Mo complexes. An example is provided where the catalyst is prepared in situ (catalyst isolation not needed) to afford secondary amines that cannot be prepared by alternative methods. [reaction: see text]
ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
The scaling of the cubic nonlinearity gamma with chain length in polyenic molecules has received ... more The scaling of the cubic nonlinearity gamma with chain length in polyenic molecules has received considerable theoretical attention. Earlier experimental investigations have been restricted to oligomers with fewer than 20 double bonds because of problems associated with the synthesis and solubility of conjugated molecules. These synthetic difficulties have been overcome in the present study by the use of modern living
Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxi... more Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph4C6H (STPP) and S-2,6-(mesityl)2C6H3 (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was Z-selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes.
Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathe... more Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathesis (ARCM) with 2-5 mol % chiral Mo complexes. An example is provided where the catalyst is prepared in situ (catalyst isolation not needed) to afford secondary amines that cannot be prepared by alternative methods. [reaction: see text]
The reaction of [W(=O)(=CHCMe2Ph)(dAdPO)2], containing bulky 2,6-diadamantyl aryloxide ligands, w... more The reaction of [W(=O)(=CHCMe2Ph)(dAdPO)2], containing bulky 2,6-diadamantyl aryloxide ligands, with partially dehydroxylated silica selectively yields a well-defined silica-supported alkylidene complex, [(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)]. This fully characterized material is a very active and stable alkene metathesis catalyst, thus allowing loadings as low as 50 ppm in the metathesis of internal alkenes. [(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)] also efficiently catalyzes the homocoupling of terminal alkenes, with turnover numbers exceeding 75,000 when ethylene is constantly removed to avoid the formation of the less reactive square-based pyramidal metallacycle resting state.
The reaction between Mo(C-t-Bu)(dme)Clâ (dme = 1,2-dimethoxyethane) and MeâSiNHAr (Ar = 2,6-diiso... more The reaction between Mo(C-t-Bu)(dme)Clâ (dme = 1,2-dimethoxyethane) and MeâSiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr)Clâ(dme) (1), which upon treatment with a catalytic amount of NEtâ is transformed into Mo(CH-t-Bu)(NAr)Clâ(dme) (2). Complexes of the type Mo(CH-t-Bu)(NAr)(OR)â (OR = OCMe(CFâ)â, OCMeâ(CFâ), O-t-Bu, or OAr) have been prepared from 2. Complexes of the type Mo(C-t-Bu)(NHAr)(OR)â (OR = OCMe(CFâ)â or OAr) have been prepared from
... 13) Cloke, FGN; Hitchcock ... The reaction mixture was stirred for 1 h in a 0 °C bath, and th... more ... 13) Cloke, FGN; Hitchcock ... The reaction mixture was stirred for 1 h in a 0 °C bath, and the reaction was quenched by addition of HCl in diethyl ether (4 mL, 1.0 M). Most of the solvent was removed at 15 Torr (water aspirator) and 45 °C. The viscous oil was dried at 100 mTorr at 50 ...
Osmium tetraoxide reacts with 3 equiv of 2,6-diisopropylphenyl isocyanate in refluxing heptane ov... more Osmium tetraoxide reacts with 3 equiv of 2,6-diisopropylphenyl isocyanate in refluxing heptane over a period of 20 h to afford red-brown crystalline trigonal planar Os(NAr)[sub 3] (1; Ar = 2,6-C[sub 6]H[sub 3]-i-Pr[sub 2]) in modest (50%) yield. 1 reacts with relatively small phosphines and phosphites to afford square-planar complexes of the type trans-Os(NAr)[sub 2]L[sub 2] (4; L = PMe[sub 2]Ph,
[506443-55-6] C44H59MoNO2 (MW 729.90) InChI = 1S/C24H34O2.C10H15N.C10H12.Mo/c1-13-11-17(23(5,6)7)... more [506443-55-6] C44H59MoNO2 (MW 729.90) InChI = 1S/C24H34O2.C10H15N.C10H12.Mo/c1-13-11-17(23(5,6)7)21(25)19(15(13)3)20-16(4)14(2)12-18(22(20)26)24(8,9)10;11-10-4-7-1-8(5-10)3-9(2-7)6-10;1-10(2,3)9-7-5-4-6-8-9;/h11-12,25-26H,1-10H3;7-9H,1-6H2;1,4-8H,2-3H3;/q;;;+2/p-2/t;7-,8+,9-,10-;;InChIKey = HCKDLEPUKVGKLH-PVFISKEKSA-LSolubility: soluble in diethyl ether, benzene, n-pentane, dichloromethane, and most organic solvents.Form SuSpplied in: light yellow powder.Purification: recrystallized under an inert atmosphere from n-pentane at −30 °C. The n-pentane is generally rendered ‘olefin-free’ by repeated stirring over sulfuric acid until the addition of acid no longer results in discoloration; it is subsequently washed with deionized water and a saturated aqueous solution of NaHCO3 followed by normal purification.Handling, Storage, and Precautions: air and moisture sensitive. The complex should be stored at, or below, −20 °C and under an inert atmosphere (N2 or Ar). Solvents should be distill...
Two diastereomers of the monoalkoxidepyrrolide (MAP) species, W(NAr)(CH(2))(Me(2)Pyr)(OR*) (1; Ar... more Two diastereomers of the monoalkoxidepyrrolide (MAP) species, W(NAr)(CH(2))(Me(2)Pyr)(OR*) (1; Ar = 2,6-diisopropylphenyl, Me(2)Pyr = 2,5-dimethylpyrrolide, OR* = (R)-3,3'-dibromo-2'-(tert-butyldimethylsilyloxy)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2-olate), were generated through addition of R*OH to W(NAr)(CH(2))(Me(2)Pyr)(2). The unsubstituted tungstacyclobutane species, W(NAr)(C(3)H(6))(Me(2)Pyr)(OR*) (2), was isolated by treating the mixture of diastereomers of 1 with ethylene. An X-ray study revealed 2 to have a trigonal bipyramidal structure in which the imido and phenoxide ligands are in axial positions. A variety of NMR experiments were carried out on 1 and 2. The major findings are the following: (i) the methylidene ligands in the two diastereomers of 1 rotate readily about the W horizontal lineC bond (k = 2-7 s(-1) at 22 degrees C); (ii) NMR studies are consistent with 2 breaking up to give an intermediate alkylidene/ethylene complex, (R)- and (S)-W(CH(2))(C(2)H(4)); and (iii) the ethylene in the (R)-W(CH(2))(C(2)H(4)) intermediate can rotate about the W-ethylene bond axis at approximately the same rate as 2 re-forms or ethylene is lost to give 1. Compound 1 reacts with trimethylphosphine to yield (R)-1(PMe(3)). Two intermediate PMe(3) adducts were observed and found to convert to (R)-1(PMe(3)) in an intramolecular fashion with an average rate constant at 5 degrees C of approximately 1.4 x 10(-4) s(-1). Both neophylidene (4) and methylidene (5) MAP species containing 2,3,5,6-tetraphenylphenoxide ligand also were prepared. Compound 5 can be heated to 80 degrees C, where methylidene rotation about the W=C bond is facile and observable in a variable-temperature (1)H NMR spectrum. A (1)H-(1)H EXSY spectrum of 5 in benzene-d(6) at 20 degrees C showed that the methylidene protons are exchanging with k = 90 s(-1). A structure of 5(THF) showed it to be a square pyramid with the methylidene ligand in the apical position and THF coordinated trans to the imido…
... Scheme 2) and 3; 4a was previously pre-pared by a two-step synthesis requiring 11 weeks.[291 ... more ... Scheme 2) and 3; 4a was previously pre-pared by a two-step synthesis requiring 11 weeks.[291 Phos-phaalkenes such as 4a are readily identified by their charac-teristic low-field 31P and I3C chemical shifts and diagnostic 'Jcp coupling", 21 ... 161 A. H. Cowley, AR Barron, Ace. ...
ABSTRACT Grafting [Mo(NAr)(CHCMe2R1)(NR2)(2)] on SiO2-(700) gives [(SiO)Mo(NAr)(CHCMe2R1)(NR2)] a... more ABSTRACT Grafting [Mo(NAr)(CHCMe2R1)(NR2)(2)] on SiO2-(700) gives [(SiO)Mo(NAr)(CHCMe2R1)(NR2)] as a major surface species along with [(SiO)Mo(NAr)(CH2CMe2R1)(NR2)(2)] according to mass balance analysis, IR and NMR spectroscopies. The replacement of one amido group by a siloxy group from the surface of silica dramatically increased the activity of the Mo complex in olefin metathesis, and tuning the imido ligands allows the reactivity to be increased by at least one order of magnitude so that an overall turnover of 231 000 can be achieved in the metathesis of propene. Additionally, ethyl oleate can also be converted into a thermodynamic equilibrated mixture in 8 h with only 0.02% of catalyst.
Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathe... more Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathesis (ARCM) with 2-5 mol % chiral Mo complexes. An example is provided where the catalyst is prepared in situ (catalyst isolation not needed) to afford secondary amines that cannot be prepared by alternative methods. [reaction: see text]
ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
The scaling of the cubic nonlinearity gamma with chain length in polyenic molecules has received ... more The scaling of the cubic nonlinearity gamma with chain length in polyenic molecules has received considerable theoretical attention. Earlier experimental investigations have been restricted to oligomers with fewer than 20 double bonds because of problems associated with the synthesis and solubility of conjugated molecules. These synthetic difficulties have been overcome in the present study by the use of modern living
Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxi... more Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph4C6H (STPP) and S-2,6-(mesityl)2C6H3 (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was Z-selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes.
Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathe... more Carbocyclic amines are synthesized efficiently in up to 93% ee by asymmetric ring-closing metathesis (ARCM) with 2-5 mol % chiral Mo complexes. An example is provided where the catalyst is prepared in situ (catalyst isolation not needed) to afford secondary amines that cannot be prepared by alternative methods. [reaction: see text]
The reaction of [W(=O)(=CHCMe2Ph)(dAdPO)2], containing bulky 2,6-diadamantyl aryloxide ligands, w... more The reaction of [W(=O)(=CHCMe2Ph)(dAdPO)2], containing bulky 2,6-diadamantyl aryloxide ligands, with partially dehydroxylated silica selectively yields a well-defined silica-supported alkylidene complex, [(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)]. This fully characterized material is a very active and stable alkene metathesis catalyst, thus allowing loadings as low as 50 ppm in the metathesis of internal alkenes. [(≡SiO)W(=O)(=CHCMe2Ph)(dAdPO)] also efficiently catalyzes the homocoupling of terminal alkenes, with turnover numbers exceeding 75,000 when ethylene is constantly removed to avoid the formation of the less reactive square-based pyramidal metallacycle resting state.
The reaction between Mo(C-t-Bu)(dme)Clâ (dme = 1,2-dimethoxyethane) and MeâSiNHAr (Ar = 2,6-diiso... more The reaction between Mo(C-t-Bu)(dme)Clâ (dme = 1,2-dimethoxyethane) and MeâSiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr)Clâ(dme) (1), which upon treatment with a catalytic amount of NEtâ is transformed into Mo(CH-t-Bu)(NAr)Clâ(dme) (2). Complexes of the type Mo(CH-t-Bu)(NAr)(OR)â (OR = OCMe(CFâ)â, OCMeâ(CFâ), O-t-Bu, or OAr) have been prepared from 2. Complexes of the type Mo(C-t-Bu)(NHAr)(OR)â (OR = OCMe(CFâ)â or OAr) have been prepared from
... 13) Cloke, FGN; Hitchcock ... The reaction mixture was stirred for 1 h in a 0 °C bath, and th... more ... 13) Cloke, FGN; Hitchcock ... The reaction mixture was stirred for 1 h in a 0 °C bath, and the reaction was quenched by addition of HCl in diethyl ether (4 mL, 1.0 M). Most of the solvent was removed at 15 Torr (water aspirator) and 45 °C. The viscous oil was dried at 100 mTorr at 50 ...
Osmium tetraoxide reacts with 3 equiv of 2,6-diisopropylphenyl isocyanate in refluxing heptane ov... more Osmium tetraoxide reacts with 3 equiv of 2,6-diisopropylphenyl isocyanate in refluxing heptane over a period of 20 h to afford red-brown crystalline trigonal planar Os(NAr)[sub 3] (1; Ar = 2,6-C[sub 6]H[sub 3]-i-Pr[sub 2]) in modest (50%) yield. 1 reacts with relatively small phosphines and phosphites to afford square-planar complexes of the type trans-Os(NAr)[sub 2]L[sub 2] (4; L = PMe[sub 2]Ph,
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