Synthesis, bonding and dynamic behavior of fac-[Mo(II)(CO)2(η3-allyl)] derivatives

J. R. Ascenso; C. G. De Azevedo; M. J. Calhorda; M. A.A.F. De; P. Costa; A. R. Dias; M. G.B. Drew; V. Félix; A. M. Galvão; C. C. Romão

doi:10.1016/S0022-328X(01)00988-3

Synthesis, bonding and dynamic behavior of fac-[Mo(II)(CO)₂(η³-allyl)] derivatives

J. R. Ascenso^*, C. G. De Azevedo, M. J. Calhorda, M. A.A.F. De, P. Costa, A. R. Dias, M. G.B. Drew, V. Félix, A. M. Galvão, C. C. Romão

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

Abstract

Cationic complexes [Mo(η³-allyl)(CO)₂(L-L)L′]PF₆, (L-L=C₆H₅SCH₂CH₂SC₆H ₅, L′=NCCH₃ (1); bipy, NCCH₃ (2); py, (NCCH₃)₂ (3); (NCCH₃)₃ (4); dppe, NCCH₃ (5) and the neutral analogues [Mo(η³-allyl)(CO)₂(L-L)X] (L-L=phen (6); bipy (7); X=Br) were synthesized. Complexes 2, 5, 6 and 7 were characterized by single crystal X-ray diffraction. Depending on the chelating ligand, these pseudo-octahedral complexes undergo different dynamic processes in solution and NMR spectroscopic evidence was provided for those studies. The structural trends of the limiting structures depicted by these complexes as well as the pathways to their inter-conversion were analyzed by ab initio theoretical calculations. Both NMR data and the calculations showed that for complex 2 the equatorial species predominates at room temperature but that two forms differing only by the conformation of the allyl coexist. Lowering the temperature leads to the appearance of the equatorial-axial isomer.

Original language	English (US)
Pages (from-to)	197-208
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	632
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(01)00988-3
State	Published - Aug 24 2001
Externally published	Yes

Keywords

Ab initio calculations
Allylic complexes
Dynamic NMR
Molybdenum
X-ray diffraction

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(01)00988-3

Cite this

@article{a2a02a9d5fc848cda61af623bb49f24b,

title = "Synthesis, bonding and dynamic behavior of fac-[Mo(II)(CO)2(η3-allyl)] derivatives",

abstract = "Cationic complexes [Mo(η3-allyl)(CO)2(L-L)L′]PF6, (L-L=C6H5SCH2CH2SC6H 5, L′=NCCH3 (1); bipy, NCCH3 (2); py, (NCCH3)2 (3); (NCCH3)3 (4); dppe, NCCH3 (5) and the neutral analogues [Mo(η3-allyl)(CO)2(L-L)X] (L-L=phen (6); bipy (7); X=Br) were synthesized. Complexes 2, 5, 6 and 7 were characterized by single crystal X-ray diffraction. Depending on the chelating ligand, these pseudo-octahedral complexes undergo different dynamic processes in solution and NMR spectroscopic evidence was provided for those studies. The structural trends of the limiting structures depicted by these complexes as well as the pathways to their inter-conversion were analyzed by ab initio theoretical calculations. Both NMR data and the calculations showed that for complex 2 the equatorial species predominates at room temperature but that two forms differing only by the conformation of the allyl coexist. Lowering the temperature leads to the appearance of the equatorial-axial isomer.",

keywords = "Ab initio calculations, Allylic complexes, Dynamic NMR, Molybdenum, X-ray diffraction",

author = "Ascenso, {J. R.} and {De Azevedo}, {C. G.} and Calhorda, {M. J.} and De, {M. A.A.F.} and P. Costa and Dias, {A. R.} and Drew, {M. G.B.} and V. F{\'e}lix and Galv{\~a}o, {A. M.} and Rom{\~a}o, {C. C.}",

note = "Funding Information: MJC and PC thank the TMR Transition Metal Clusters in Catalysis and Organic Synthesis. VF acknowledges FCT and the British Council for funding. The University of Reading and EPSRC are thanked for funds for the Image Plate system.",

year = "2001",

month = aug,

day = "24",

doi = "10.1016/S0022-328X(01)00988-3",

language = "English (US)",

volume = "632",

pages = "197--208",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

T1 - Synthesis, bonding and dynamic behavior of fac-[Mo(II)(CO)2(η3-allyl)] derivatives

AU - Ascenso, J. R.

AU - De Azevedo, C. G.

AU - Calhorda, M. J.

AU - De, M. A.A.F.

AU - Costa, P.

AU - Dias, A. R.

AU - Drew, M. G.B.

AU - Félix, V.

AU - Galvão, A. M.

AU - Romão, C. C.

N1 - Funding Information: MJC and PC thank the TMR Transition Metal Clusters in Catalysis and Organic Synthesis. VF acknowledges FCT and the British Council for funding. The University of Reading and EPSRC are thanked for funds for the Image Plate system.

PY - 2001/8/24

Y1 - 2001/8/24

N2 - Cationic complexes [Mo(η3-allyl)(CO)2(L-L)L′]PF6, (L-L=C6H5SCH2CH2SC6H 5, L′=NCCH3 (1); bipy, NCCH3 (2); py, (NCCH3)2 (3); (NCCH3)3 (4); dppe, NCCH3 (5) and the neutral analogues [Mo(η3-allyl)(CO)2(L-L)X] (L-L=phen (6); bipy (7); X=Br) were synthesized. Complexes 2, 5, 6 and 7 were characterized by single crystal X-ray diffraction. Depending on the chelating ligand, these pseudo-octahedral complexes undergo different dynamic processes in solution and NMR spectroscopic evidence was provided for those studies. The structural trends of the limiting structures depicted by these complexes as well as the pathways to their inter-conversion were analyzed by ab initio theoretical calculations. Both NMR data and the calculations showed that for complex 2 the equatorial species predominates at room temperature but that two forms differing only by the conformation of the allyl coexist. Lowering the temperature leads to the appearance of the equatorial-axial isomer.

AB - Cationic complexes [Mo(η3-allyl)(CO)2(L-L)L′]PF6, (L-L=C6H5SCH2CH2SC6H 5, L′=NCCH3 (1); bipy, NCCH3 (2); py, (NCCH3)2 (3); (NCCH3)3 (4); dppe, NCCH3 (5) and the neutral analogues [Mo(η3-allyl)(CO)2(L-L)X] (L-L=phen (6); bipy (7); X=Br) were synthesized. Complexes 2, 5, 6 and 7 were characterized by single crystal X-ray diffraction. Depending on the chelating ligand, these pseudo-octahedral complexes undergo different dynamic processes in solution and NMR spectroscopic evidence was provided for those studies. The structural trends of the limiting structures depicted by these complexes as well as the pathways to their inter-conversion were analyzed by ab initio theoretical calculations. Both NMR data and the calculations showed that for complex 2 the equatorial species predominates at room temperature but that two forms differing only by the conformation of the allyl coexist. Lowering the temperature leads to the appearance of the equatorial-axial isomer.

KW - Ab initio calculations

KW - Allylic complexes

KW - Dynamic NMR

KW - Molybdenum

KW - X-ray diffraction

UR - http://www.scopus.com/inward/record.url?scp=0001304142&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(01)00988-3

DO - 10.1016/S0022-328X(01)00988-3

M3 - Article

AN - SCOPUS:0001304142

SN - 0022-328X

VL - 632

SP - 197

EP - 208

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -