TY - JOUR
T1 - Metallacumulenylidene complexes in the cycloheptatrienyl molybdenum series [Mo{(C)n=CR2}L2(η-C7H 7)]+ (n = 0-2; L2 = P-Donor Ligand). X-ray crystal structures of [Mo{C=C(H)Ph}{P(OMe)3}2(η-C 7H7)][BF4]and [Mo(C=C=CPh2)(dppe) (η7-C...
AU - Grime, Richard W.
AU - Helliwell, Madeleine
AU - Hussain, Zaffar I.
AU - Lancashire, Hannah N.
AU - Mason, Christopher R.
AU - McDouall, Joseph J W
AU - Mydlowski, Christopher M.
AU - Whiteley, Mark W.
N1 - CAN 148:379715 29-11 Organometallic and Organometalloidal Compounds Journal 0276-7333 written in English. 1013394-53-0P; 1013394-54-1P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (crystal structure; prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 1013394-48-3P; 1013394-50-7P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (mol. structure; prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 1013394-62-1P Role: BYP (Byproduct), PREP (Preparation) (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 2143-69-3 (Ethenylidene); 70571-89-0 (1,2,3-Butatrien-1-ylidene); 121195-06-0; 129066-04-2 (1,2,3,4-Pentatetraenylidene); 171415-71-7; 404835-25-2; 849148-92-1; 1013394-51-8; 1013394-58-5; 1013394-59-6 Role: PRP (Properties) (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 1013394-52-9P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 127-66-2 (2-Phenyl-3-butyn-2-ol); 536-74-3 (Phenylethyne); 927-74-2 (3-Butyn-1-ol); 3923-52-2 (1,1-Diphenyl-2-propyn-1-ol); 5390-04-5 (4-Pentyn-1-ol); 10147-11-2 (3-Phenyl-1-propyne); 16520-62-0 (4-Phenyl-1-butyne); 52326-38-2 ((h7-Cycloheptatrienyl)(h6-toluene)molybdenum hexafluorophosphate); 53556-07-3 (Bromodicarbonylcycloheptatrienylmolybdenum); 123384-16-7 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 183135-34-4P; 1013394-56-3P; 1013394-57-4P; 1013394-60-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations); 183135-22-0P; 183135-24-2P; 183135-28-6P; 183135-30-0P; 1013394-44-9P; 1013394-46-1P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations)
PY - 2008/3/10
Y1 - 2008/3/10
N2 - Title full: Metallacumulenylidene complexes in the cycloheptatrienyl molybdenum series [Mo{(C)n=CR2}L2(η-C7H 7)]+ (n = 0-2; L2 = P-Donor Ligand). X-ray crystal structures of [Mo{C=C(H)Ph}{P(OMe)3}2(η-C 7H7)][BF4]and [Mo(C=C=CPh2)(dppe) (η7-C7H7)][PF6] and DFT investigation of cumulenylidene ligand orientations. A series of metallacumulenylidene complexes of the cycloheptatrienyl molybdenum auxiliary [Mo{(C)n=CR2}L2(η- C7H7)]+ (n = 0-2; L2 = P-donor ligand) have been synthesized by reaction of [MoXL2(η-C 7H7)] (X = Br, L2 = Ph2PCH 2CH2PPh2 (dppe); X -1, L2 = 2P(OMe)3) or [Mo(OCMe2)L2(η-C 7H7)]+ (L2 = dppe, Ph 2PCH2PPh2 (dppm)) with the terminal alkynes HC=CR; use of [MoBr(dppe)(ηC7H7)] as a precursor is facilitated by an improved, one-step synthesis from [MoBr(CO) 2(η-C7H7)]. Syntheses of the 2-oxacyclocarbene complexes [Mo(CCH2CH2(CH 2)xO)L2(η-C7H7)] + (x = 1, L2 = dppm (1), dppe (2); x = 2, L2 = dppm (3), L2 = dppe (4)), the vinylidenes [Mo{C=C(H)(CH 2)2CH2OH}(dppe)(η-C7H 7)][PF6] (5), [Mo{C=C(H)(CH2) xPh}(dppe)(η-C7H7)]+(x=2(6), 1 (7)), and [Mo(C=C(H)Ph) (P(OMe)3}2(η-C 7H7)]+ (8), and the first examples of monometallic molybdenum allenylidene complexes, [Mo(C=C=CRPh)-(dppe)(η- C7H7)]+ (R = Ph (9), Me (10)) are reported. X-ray structural studies on complexes 8 and 9 have determined Mo-C α distances as follows: 8, 1.929(3) Å 9, 1.994(3) Å. In 8, the vinylidene ligand substituents lie in the pseudo mirror plane of the MoL2(η-C7H7) auxiliary (vertical orientation) with the phenyl group located syn to the cycloheptatrienyl ring, whereas the allenylidene ligand substituents of 9 are perpendicular to the pseudo mirror plane (horizontal orientation). This series of atypical orientations of cumulenylidene ligand substituents, imposed by the cycloheptatrienyl molybdenum auxiliary, has been investigated further by variable-temperature NMR spectroscopy and quantum-chemical theoretical calculations. A DFT analysis of the complexes [Mo(C=CH2)(dppe)(η- C7H7)]+ (11), [Ru(C=CH2) (dppe)Cp]+ (12), and [Mo(C=C=CMePh)(dppe)(η-C7H 7)]+ (10) concurs with experimentally determined cumulenylidene ligand orientations. A separate analysis of the fragments [Mo(dppe)(η-C7H7)]+ and [Ru(dppe)Cp] + reveals that the HOMO of the [Mo(dppe)(η-C7H 7)]+ fragment includes a significant contribution from the metal dz2 orbital, whereas the HOMO of the [Ru(dppe)Cp]+ fragment is based on a metal dxy orbital, orthogonal- to the HOMO of the [Mo(dppe)(η-C7H 7)]+ unit. In cumulenylidene complexes of the Mo(dppe)(η-C7H7) auxiliary, interactions between the dz2-based HOMO of the metal fragment and the vacant LUMO of the cumulenylidene ligand dominate the control of ligand orientation and thus account for the observed structures. © 2008 American Chemical Society.
AB - Title full: Metallacumulenylidene complexes in the cycloheptatrienyl molybdenum series [Mo{(C)n=CR2}L2(η-C7H 7)]+ (n = 0-2; L2 = P-Donor Ligand). X-ray crystal structures of [Mo{C=C(H)Ph}{P(OMe)3}2(η-C 7H7)][BF4]and [Mo(C=C=CPh2)(dppe) (η7-C7H7)][PF6] and DFT investigation of cumulenylidene ligand orientations. A series of metallacumulenylidene complexes of the cycloheptatrienyl molybdenum auxiliary [Mo{(C)n=CR2}L2(η- C7H7)]+ (n = 0-2; L2 = P-donor ligand) have been synthesized by reaction of [MoXL2(η-C 7H7)] (X = Br, L2 = Ph2PCH 2CH2PPh2 (dppe); X -1, L2 = 2P(OMe)3) or [Mo(OCMe2)L2(η-C 7H7)]+ (L2 = dppe, Ph 2PCH2PPh2 (dppm)) with the terminal alkynes HC=CR; use of [MoBr(dppe)(ηC7H7)] as a precursor is facilitated by an improved, one-step synthesis from [MoBr(CO) 2(η-C7H7)]. Syntheses of the 2-oxacyclocarbene complexes [Mo(CCH2CH2(CH 2)xO)L2(η-C7H7)] + (x = 1, L2 = dppm (1), dppe (2); x = 2, L2 = dppm (3), L2 = dppe (4)), the vinylidenes [Mo{C=C(H)(CH 2)2CH2OH}(dppe)(η-C7H 7)][PF6] (5), [Mo{C=C(H)(CH2) xPh}(dppe)(η-C7H7)]+(x=2(6), 1 (7)), and [Mo(C=C(H)Ph) (P(OMe)3}2(η-C 7H7)]+ (8), and the first examples of monometallic molybdenum allenylidene complexes, [Mo(C=C=CRPh)-(dppe)(η- C7H7)]+ (R = Ph (9), Me (10)) are reported. X-ray structural studies on complexes 8 and 9 have determined Mo-C α distances as follows: 8, 1.929(3) Å 9, 1.994(3) Å. In 8, the vinylidene ligand substituents lie in the pseudo mirror plane of the MoL2(η-C7H7) auxiliary (vertical orientation) with the phenyl group located syn to the cycloheptatrienyl ring, whereas the allenylidene ligand substituents of 9 are perpendicular to the pseudo mirror plane (horizontal orientation). This series of atypical orientations of cumulenylidene ligand substituents, imposed by the cycloheptatrienyl molybdenum auxiliary, has been investigated further by variable-temperature NMR spectroscopy and quantum-chemical theoretical calculations. A DFT analysis of the complexes [Mo(C=CH2)(dppe)(η- C7H7)]+ (11), [Ru(C=CH2) (dppe)Cp]+ (12), and [Mo(C=C=CMePh)(dppe)(η-C7H 7)]+ (10) concurs with experimentally determined cumulenylidene ligand orientations. A separate analysis of the fragments [Mo(dppe)(η-C7H7)]+ and [Ru(dppe)Cp] + reveals that the HOMO of the [Mo(dppe)(η-C7H 7)]+ fragment includes a significant contribution from the metal dz2 orbital, whereas the HOMO of the [Ru(dppe)Cp]+ fragment is based on a metal dxy orbital, orthogonal- to the HOMO of the [Mo(dppe)(η-C7H 7)]+ unit. In cumulenylidene complexes of the Mo(dppe)(η-C7H7) auxiliary, interactions between the dz2-based HOMO of the metal fragment and the vacant LUMO of the cumulenylidene ligand dominate the control of ligand orientation and thus account for the observed structures. © 2008 American Chemical Society.
KW - Carbene complexes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (Group VIB element complexes, cumulenylidene
KW - prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations)
KW - Carbene complexes
KW - Metallocenes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (Group VIB element complexes
KW - Group VIB element complexes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (carbene complexes, cumulenylidene
KW - Group VIB element complexes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (carbene complexes
KW - NMR (carbon-13
KW - Sandwich compounds Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (half-sandwich, cycloheptatrienylmolybdenum
KW - Group VIB element complexes Role: PRP (Properties), RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (metallocenes
KW - Crystal structure
KW - Molecular structure (of cycloheptatrienyl molybdenum vinylidene and allenylidene complexes)
KW - Molecular structure (optimized
KW - of cycloheptatrienylmolybdenum and cyclopentadienylruthenium carbene, vinylidene and allenylidene complexes)
KW - NMR (phosphorus-31
KW - Conformation
KW - HOMO
KW - LUMO
KW - NMR
KW - Rotamers
KW - Rotational barrier (prepn. and structure of cycloheptatrienylmolybdenum oxacyclocarbenes, vinylidenes and allenylidenes via cycloheptatrienylmolybdenum complexes and terminal alkynes and DFT study of cumulenylidene orientations)
KW - Alkynes Role: RCT (Reactant), RACT (Reactant or reagent) (alpha -
KW - bromodicarbonylcycloheptatrienylmolybdenum reaction dppe dppm terminal alkyne
KW - cycloheptatrienyltoluenemolybdenum hexafluorophosphate reaction dppe dppm terminal alkyne cyclization
KW - cycloheptatrienyliodomolybdenum bisphosphite reaction terminal alkyne
KW - cycloheptatrienylmolybdenum oxacyclocarbene vinylidene allenylidene prepn
KW - crystal mol structure cycloheptatrienylmolybdenum vinylidene allenylidene conformation prepn
KW - mol structure optimized cycloheptatrienylmolybdenum cyclopentadienylruthenium carbene cumulenylidene MO conformation
U2 - 10.1021/om700920t
DO - 10.1021/om700920t
M3 - Article
SN - 0276-7333
VL - 27
SP - 857
EP - 871
JO - Organometallics
JF - Organometallics
IS - 5
ER -