Synthesis and substitution reactions of a heterodimetallic molybdenum–manganese complex, [MoMn(µ-H)(µ-PPh2)(η5-C5H5)(CO)6]; X-ray crystal structure of [MoMn(µ-H)(µ-PPh2)(η5-C5H5)(CO)4(dppm-PP′)]

Horton, Andrew D.; Mays, Martin J.; Raithby, Paul R.

doi:10.1039/dt9870001557

Cited by 23 publications

(13 citation statements)

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“…The adoption of the dibasal geometry may be favoured in order to minimise adverse steric interactions between the phenyl rings and dithiolate-bridge. The biteangle of 74.55(4)°for the diphosphine in 3 is very small, but in line with values found in dppm-chelate complexes [16,17]. Its adoption requires a significant decrease in the preferred dibasal angle as can be seen when compared with that at the unsubstituted iron centre [C(3)-Fe(2)-C(4) 90.85 (19)°] [4a].…”

Section: With Bis(diphenylphosphino)methane (Dppm)mentioning

confidence: 73%

“…Its adoption requires a significant decrease in the preferred dibasal angle as can be seen when compared with that at the unsubstituted iron centre [C(3)-Fe(2)-C(4) 90.85 (19)°] [4a]. There is also a significant reduction in the P-C-P angle to 93.53 (17)°upon chelation which can be compared with that of 114.3(2)°in 2. In 3 this leads to the close contact of the two phosphorus nuclei [P(1)-P(2) 2.6854 (12) Å ] when compared to that in the 2 [P(1)-P(2) 3.094(3) Å ].…”

Section: With Bis(diphenylphosphino)methane (Dppm)mentioning

confidence: 97%

“…In 3 the diphosphine binds to a single iron atom occupying the two basal positions and rendering the two dithiolatebridges equivalent and while in 2 the two sulphurs bind approximately symmetrically to the two iron atoms, in 3 they are quite asymmetric, lying closer to the phosphine bound metal centre [Fe(1)-S(av) 2.224 (2), Fe(2)-S(av) 2.263(2) Å ]. While there are a number of examples of dppm acting in a chelating manner in polynuclear complexes containing the larger second and third row transition metals [16], the only crystallographically characterised example of this behaviour at a first row metal centre is in [CpMo-(CO) 2 (l-H)(l-PPh 2 )Mn(j 2 -dppm)(CO) 2 ] [17].…”

Section: With Bis(diphenylphosphino)methane (Dppm)mentioning

confidence: 99%

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Models of the iron-only hydrogenase: Reactions of [Fe2(CO)6(μ-pdt)] with small bite-angle diphosphines yielding bridge and chelate diphosphine complexes [Fe2(CO)4(diphosphine)(μ-pdt)]

Adam

Hogarth

Richards

2007

Journal of Organometallic Chemistry

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Section: With Bis(diphenylphosphino)methane (Dppm)mentioning

confidence: 73%

Section: With Bis(diphenylphosphino)methane (Dppm)mentioning

confidence: 97%

Section: With Bis(diphenylphosphino)methane (Dppm)mentioning

confidence: 99%

See 1 more Smart Citation

Models of the iron-only hydrogenase: Reactions of [Fe2(CO)6(μ-pdt)] with small bite-angle diphosphines yielding bridge and chelate diphosphine complexes [Fe2(CO)4(diphosphine)(μ-pdt)]

Adam

Hogarth

Richards

2007

Journal of Organometallic Chemistry

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“…71 The procedure can also be used for the synthesis of [(r|-Cp)Ru(CO)-(H-H)(|Li-PPh 2 )Mn(CO) 4 ]; this is one of six products obtained in the photolysis of [(OC) 5 MnRu(CO) 2 (r|-Cp)] in the presence of PPh 2 H. 72 In situ formation of [Pd(NCPh) 2 {Mn(CO) 5 (6)). 77 When [Mn(Me)(CO) 5 ] is used in the latter reaction system, [Mn(CO) 4 (u-COMe)(u-PPh 2 )Fe(CO)(r|-Cp)] is formed as the product.…”

Section: (U-h)(u-pph 2 )Mo(co) 2 (R|-cp)] From Pph 2 H and [Mn(co) 5 mentioning

confidence: 97%

Manganese Complexes Containing Nonmetallic Elements

Treichel

1995

Comprehensive Organometallic Chemistry II

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“…In addition to seven 13C0 resonances the undecoupled spectrum at 298 K showed one doublet at 6 89.60 [J(CH) 157. 8 Hz] and two triplets at 6 50.1 [ J ( C H ) 153.6 Hz] and 6 49.2 [J(CH) 156.2 Hz] due respectively to the central and two terminal carbon atoms of the allyl ligand. In the structure of the related molybdenum-manganese complex [(q-C,H,)-…”

Section: Plex [Mn { ~-O:~~-c(p~)=c(h)p~)(~-pp~)(co)(cnbu')]~mentioning

confidence: 99%

Dinuclear allyl and µ-vinyl complexes from the reactions of a µ-hydrido dimanganese and a µ-hydrido manganese–molybdenum complex with alkynes containing α-methyl or α-methylene substituents

Horton¹,

Kemball²,

Mays³

1988

J. Chem. Soc., Dalton Trans.

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The photolytic reactions of [Mn,(p-H) (p-PPh,) (CO),] and of [(q-C,H,) (CO),Mo(p-H) -(p-PPh,) M n ( CO),] with alkynes containing a-methyl or a-methylene substituents have been studied. The dimanganese complex reacts with MeCECH to give, in comparable yields, the q3-allyl complex [Mn,(p-PPh,) (q3-C3H5) (CO),] and an inseparable mixture of the two p-vinyl complexes [Mn(p-PPh,),{p-o:q2-C( Me)=CH,}(CO),] and [Mn,{p-o:q2-C(H)=C(H)Me}(p-PPh,) (CO),]. With MeCzCMe, [Mn,(p-PPh,)(q3-syn-MeCHCHCH,) (CO),] and [Mn,{p-o:q2-C( Me)=C( H)Me}(p-PPh,) (CO),] are obtained, again in comparable yields. Reactions of the dimanganese complex with EtCrCH and PhC-CMe proceed analogously. The molybdenummanganese complex does not give p-vinyl complexes on reaction with MeCrCH, MeCrCMe, or E t C K H . Instead MeCrCH gives [(CO),] as the sole product whereas M e C r C M e and EtCGCH both give the same inseparable isomeric mixture of [ (q -C,H,) (CO),Mo(p-PPh,) Mn(q3-syn-MeCflCHCH,) (CO),] and [ (q-C5f15) (CO),Mo(p-PPh,) -Mn(q3-anti-MeCHCHCH,) (CO),]. Deuteriation studies show that the formation of the allyl complexes from the alkynes involves a 1,2 hydrogen shift within the ligand; a mechanistic scheme for the reactions of the dimanganese and molybdenum-manganese complexes with a-methyl-and x-methylene-substituted alkynes consistent w i t h such a shift is proposed.The reactions of alkynes with dinuclear and polynuclear complexes containing p-hydrido ligands generally give, in the first instance, insertion products containing p-vinyl ligands. In a previous paper we reported that the dimanganese coniplex [Mn,(p-H)(p-PPh,)(CO),] (1) reacts in this way with RCrCR' under photolysis to give the p-vinyl complexes [Mn,(p-o:q2- C(R)=C(H)R')(p-PPh,)(CO),1.6The range of alkynes studied was, however, restricted to P h C S P h , P h C g H , and H C g H and we have now extended our investigations to alkynes containing x-methyl or a-methylene substituents. In addition to giving p-vinyl complexes such alkynes also give q3-allyl complexes by a process which must involve hydrogen transfer within the ligands. In order to explore the generality of these hydrogen-transfer reactions we have also studied the reactions of alkynes containing a-methyl or a-methylene substituents with the p-hydrido heterodimetallic complex [(q-C,H,)(CO),Mo-(p-H)(p-PPh2)Mn(C0),1 (2).738 Complexes (1) and (2) react differently with acetylene itself, the former giving a simple pvinyl complex ' whereas the latter gives, as the major product,

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Synthesis and substitution reactions of a heterodimetallic molybdenum–manganese complex, [MoMn(µ-H)(µ-PPh₂)(η⁵-C₅H₅)(CO)₆]; X-ray crystal structure of [MoMn(µ-H)(µ-PPh₂)(η⁵-C₅H₅)(CO)₄(dppm-PP′)]

Cited by 23 publications

References 1 publication

Models of the iron-only hydrogenase: Reactions of [Fe2(CO)6(μ-pdt)] with small bite-angle diphosphines yielding bridge and chelate diphosphine complexes [Fe2(CO)4(diphosphine)(μ-pdt)]

Models of the iron-only hydrogenase: Reactions of [Fe2(CO)6(μ-pdt)] with small bite-angle diphosphines yielding bridge and chelate diphosphine complexes [Fe2(CO)4(diphosphine)(μ-pdt)]

Manganese Complexes Containing Nonmetallic Elements

Dinuclear allyl and µ-vinyl complexes from the reactions of a µ-hydrido dimanganese and a µ-hydrido manganese–molybdenum complex with alkynes containing α-methyl or α-methylene substituents

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