Abstract
Complexes of the type N≡Mo(OR)3 (R = tertiary alkyl, tertiary silyl, bulky aryl) have been synthesized in the search for molybdenum-based nitrile-alkyne cross-metathesis (NACM) catalysts. Protonolysis of known N≡Mo(NMe2)3 led to the formation of N≡Mo(O-2,6-iPr2C6H3) 3(NHMe2) (12), N≡Mo(OSiPh3) 3(NHMe2) (5-NHMe2), and N≡Mo(OCPh 2Me)3(NHMe2) (17-NHMe2). The X-ray structure of 12 revealed an NHMe2 ligand bound cis to the nitrido ligand, while 5-NHMe2 possessed an NHMe2 bound trans to the nitride ligand. Consequently, 17-NHMe2 readily lost its amine ligand to form N≡Mo(OCPh2Me)3 (17), while 12 and 5-NHMe2 retained their amine ligands in solution. Starting from bulkier tris-anilide complexes, N≡Mo(N[R]Ar)3 (R = isopropyl, tert-butyl; Ar = 3,5-dimethylphenyl) allowed for the formation of base-free complexes N≡Mo(OSiPh3)3 (5) and N≡ Mo(OSiPh2 tBu)3 (16). Achievement of a NACM cycle requires the nitride complex to react with alkynes to form alkylidyne complexes; therefore the alkyne cross-metathesis (ACM) activity of the complexes was tested. Complex 5 was found to be an efficient catalyst for the ACM of 1-phenyl-1-butyne at room temperature. Complexes 12 and 5-NHMe2 were also active for ACM at 75 °C, while 17-NHMe2 and 16 did not show ACM activity. Only 5 proved to be active for the NACM of anisonitrile, which is a reactive substrate in NACM catalyzed by tungsten. NACM with 5 required a reaction temperature of 180 °C in order to initiate the requisite alkylidyne-to-nitride conversion, with slightly more than two turnovers achieved prior to catalyst deactivation. Known molybdenum nitrido complexes were screened for NACM activity under similar conditions, and only N≡Mo(OSiPh3)3(py) (5-py) displayed any trace of NACM activity.
| Original language | English |
|---|---|
| Pages (from-to) | 5936-5945 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 50 |
| Issue number | 13 |
| DOIs | |
| Publication status | Published - Jul 4 2011 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
Synthesis of molybdenum nitrido complexes for triple-bond metathesis of alkynes and nitriles. / Wiedner, Eric; Gallagher, Kimberley J.; Johnson, Marc J A; Kampf, Jeff W.
In: Inorganic Chemistry, Vol. 50, No. 13, 04.07.2011, p. 5936-5945.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis of molybdenum nitrido complexes for triple-bond metathesis of alkynes and nitriles
AU - Wiedner, Eric
AU - Gallagher, Kimberley J.
AU - Johnson, Marc J A
AU - Kampf, Jeff W.
PY - 2011/7/4
Y1 - 2011/7/4
N2 - Complexes of the type N≡Mo(OR)3 (R = tertiary alkyl, tertiary silyl, bulky aryl) have been synthesized in the search for molybdenum-based nitrile-alkyne cross-metathesis (NACM) catalysts. Protonolysis of known N≡Mo(NMe2)3 led to the formation of N≡Mo(O-2,6-iPr2C6H3) 3(NHMe2) (12), N≡Mo(OSiPh3) 3(NHMe2) (5-NHMe2), and N≡Mo(OCPh 2Me)3(NHMe2) (17-NHMe2). The X-ray structure of 12 revealed an NHMe2 ligand bound cis to the nitrido ligand, while 5-NHMe2 possessed an NHMe2 bound trans to the nitride ligand. Consequently, 17-NHMe2 readily lost its amine ligand to form N≡Mo(OCPh2Me)3 (17), while 12 and 5-NHMe2 retained their amine ligands in solution. Starting from bulkier tris-anilide complexes, N≡Mo(N[R]Ar)3 (R = isopropyl, tert-butyl; Ar = 3,5-dimethylphenyl) allowed for the formation of base-free complexes N≡Mo(OSiPh3)3 (5) and N≡ Mo(OSiPh2 tBu)3 (16). Achievement of a NACM cycle requires the nitride complex to react with alkynes to form alkylidyne complexes; therefore the alkyne cross-metathesis (ACM) activity of the complexes was tested. Complex 5 was found to be an efficient catalyst for the ACM of 1-phenyl-1-butyne at room temperature. Complexes 12 and 5-NHMe2 were also active for ACM at 75 °C, while 17-NHMe2 and 16 did not show ACM activity. Only 5 proved to be active for the NACM of anisonitrile, which is a reactive substrate in NACM catalyzed by tungsten. NACM with 5 required a reaction temperature of 180 °C in order to initiate the requisite alkylidyne-to-nitride conversion, with slightly more than two turnovers achieved prior to catalyst deactivation. Known molybdenum nitrido complexes were screened for NACM activity under similar conditions, and only N≡Mo(OSiPh3)3(py) (5-py) displayed any trace of NACM activity.
AB - Complexes of the type N≡Mo(OR)3 (R = tertiary alkyl, tertiary silyl, bulky aryl) have been synthesized in the search for molybdenum-based nitrile-alkyne cross-metathesis (NACM) catalysts. Protonolysis of known N≡Mo(NMe2)3 led to the formation of N≡Mo(O-2,6-iPr2C6H3) 3(NHMe2) (12), N≡Mo(OSiPh3) 3(NHMe2) (5-NHMe2), and N≡Mo(OCPh 2Me)3(NHMe2) (17-NHMe2). The X-ray structure of 12 revealed an NHMe2 ligand bound cis to the nitrido ligand, while 5-NHMe2 possessed an NHMe2 bound trans to the nitride ligand. Consequently, 17-NHMe2 readily lost its amine ligand to form N≡Mo(OCPh2Me)3 (17), while 12 and 5-NHMe2 retained their amine ligands in solution. Starting from bulkier tris-anilide complexes, N≡Mo(N[R]Ar)3 (R = isopropyl, tert-butyl; Ar = 3,5-dimethylphenyl) allowed for the formation of base-free complexes N≡Mo(OSiPh3)3 (5) and N≡ Mo(OSiPh2 tBu)3 (16). Achievement of a NACM cycle requires the nitride complex to react with alkynes to form alkylidyne complexes; therefore the alkyne cross-metathesis (ACM) activity of the complexes was tested. Complex 5 was found to be an efficient catalyst for the ACM of 1-phenyl-1-butyne at room temperature. Complexes 12 and 5-NHMe2 were also active for ACM at 75 °C, while 17-NHMe2 and 16 did not show ACM activity. Only 5 proved to be active for the NACM of anisonitrile, which is a reactive substrate in NACM catalyzed by tungsten. NACM with 5 required a reaction temperature of 180 °C in order to initiate the requisite alkylidyne-to-nitride conversion, with slightly more than two turnovers achieved prior to catalyst deactivation. Known molybdenum nitrido complexes were screened for NACM activity under similar conditions, and only N≡Mo(OSiPh3)3(py) (5-py) displayed any trace of NACM activity.
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U2 - 10.1021/ic1024247
DO - 10.1021/ic1024247
M3 - Article
VL - 50
SP - 5936
EP - 5945
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 13
ER -