Metallathiirenes. 3.1 thiocarbamoyl and alkoxythiocarbonyl complexes of molybdenum(II) and tungsten(II)

Stephen Anderson; Darren J. Cook; Anthony F. Hill

doi:10.1021/om991019h

Metallathiirenes. 3.¹ thiocarbamoyl and alkoxythiocarbonyl complexes of molybdenum(II) and tungsten(II)

Stephen Anderson, Darren J. Cook, Anthony F. Hill^*

^*Corresponding author for this work

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

37 Citations (Scopus)

Abstract

Synthetic routes to thiocarbamoyl (thiocarboxamide) complexes of divalent molybdenum and tungsten are reported: The reaction of fac-[Mo(CO)₃(NCMe)₃] with N,N-dimethyl thiocarbamoyl chloride (Me₂NC(=S)Cl) at low temperature provides a thermally labile intermediate (1) presumed on the basis of subsequent transformations to be [Mo(η²-SCNMe₂)-Cl(CO)₃(NCMe)]. Reactions of 1 with K[HB(pz)₃] (pz = pyrazol-1-yl), NaC₅H₅, bipy, or tmeda provide the complexes [Mo(η²-SCNMe₂)(CO)₂{HB(pz)₃}] (2), [Mo(η²-SCNMe₂)(CO)₂(η-C₅ H₅)] (3), [Mo(η²-SCNMe₂)Cl(CO)₂(bipy)] (4), and [Mo(η²-SCNMe₂)Cl(CO)₂(tmeda)] (5), respectively. The complex cis,cis,trans-[Mo(η²-SCNMe₂)Cl(CO)₂ (PPh₃)₂] (6) results from the oxidative addition of Me₂NC(=S)Cl to [Mo(NCMe)₂(CO)₂(PPh₃)₂] and is one of two isomers obtained from the reaction of 1 with PPh₃. The complex 2 may also be obtained from reaction of (i) K[Mo(CO)₃{HB(pz)₃}] with Me₂NC(=S)Cl; (ii) [Mo(CO)₃(η⁶-C₇H₈)] with Me₂NC(=S)Cl and K[HB(pz)₃]; and (iii) K[HB(pz)₃] with either 5 or 6. Sequential treatment of either [Mo(CO)₃-(NCMe)₃] or [Mo(CO)₃(η⁶-C₇H₈)] with ClC(=S)OR (R = C₆H₄Me-4, C₆H₅) and K[HB(pz)₃] provides the complexes [Mo(η²-SCOR)(CO)₂{HB(pz)₃}] [R = C₆H₄Me-4 (7a), C₆H₅ (7b)]. Attempts to prepare a mononuclear thiocarbamoyl complex by addition of elemental sulfur or propene episulfide to the aminomethylidyne complex [Mo(≡CNⁱPr₂)(CO)₂{HB(pz)₃}] (8) were unsuccessful; however addition of [Fe₂(CO)₉] to 8 provided the thermally unstable complex [MoFe(μ-CNⁱPr₂)(CO)₅{HB(pz)₃}] (9), which reacts with sulfur to provide the heterobimetallic bridging thiocarbamoyl complex [MoFe(μ-SCNⁱPr₂)(CO)₅{HB(pz)₃}] (10). Treating fac-[W(CO)₃(NCMe)₃] sequentially with Me₂NC(=S)Cl and K[HB(pz)₃] provided [W(η²-SCNMe₂)(CO)₂{HB(pz)₃}] (11); however replacing Me₂NC(=S)Cl with ClC(=S)OC₆H₄-Me-4 led to [WCl(CO)₃{HB(pz)₃}] (12).

Original language	English
Pages (from-to)	2468-2476
Number of pages	9
Journal	Organometallics
Volume	20
Issue number	12
DOIs	https://doi.org/10.1021/om991019h
Publication status	Published - 11 Jun 2001

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@article{ad5143c69b274dfca7d684c131a3dfc2,

title = "Metallathiirenes. 3.1 thiocarbamoyl and alkoxythiocarbonyl complexes of molybdenum(II) and tungsten(II)",

abstract = "Synthetic routes to thiocarbamoyl (thiocarboxamide) complexes of divalent molybdenum and tungsten are reported: The reaction of fac-[Mo(CO)3(NCMe)3] with N,N-dimethyl thiocarbamoyl chloride (Me2NC(=S)Cl) at low temperature provides a thermally labile intermediate (1) presumed on the basis of subsequent transformations to be [Mo(η2-SCNMe2)-Cl(CO)3(NCMe)]. Reactions of 1 with K[HB(pz)3] (pz = pyrazol-1-yl), NaC5H5, bipy, or tmeda provide the complexes [Mo(η2-SCNMe2)(CO)2{HB(pz)3}] (2), [Mo(η2-SCNMe2)(CO)2(η-C5 H5)] (3), [Mo(η2-SCNMe2)Cl(CO)2(bipy)] (4), and [Mo(η2-SCNMe2)Cl(CO)2(tmeda)] (5), respectively. The complex cis,cis,trans-[Mo(η2-SCNMe2)Cl(CO)2 (PPh3)2] (6) results from the oxidative addition of Me2NC(=S)Cl to [Mo(NCMe)2(CO)2(PPh3)2] and is one of two isomers obtained from the reaction of 1 with PPh3. The complex 2 may also be obtained from reaction of (i) K[Mo(CO)3{HB(pz)3}] with Me2NC(=S)Cl; (ii) [Mo(CO)3(η6-C7H8)] with Me2NC(=S)Cl and K[HB(pz)3]; and (iii) K[HB(pz)3] with either 5 or 6. Sequential treatment of either [Mo(CO)3-(NCMe)3] or [Mo(CO)3(η6-C7H8)] with ClC(=S)OR (R = C6H4Me-4, C6H5) and K[HB(pz)3] provides the complexes [Mo(η2-SCOR)(CO)2{HB(pz)3}] [R = C6H4Me-4 (7a), C6H5 (7b)]. Attempts to prepare a mononuclear thiocarbamoyl complex by addition of elemental sulfur or propene episulfide to the aminomethylidyne complex [Mo(≡CNiPr2)(CO)2{HB(pz)3}] (8) were unsuccessful; however addition of [Fe2(CO)9] to 8 provided the thermally unstable complex [MoFe(μ-CNiPr2)(CO)5{HB(pz)3}] (9), which reacts with sulfur to provide the heterobimetallic bridging thiocarbamoyl complex [MoFe(μ-SCNiPr2)(CO)5{HB(pz)3}] (10). Treating fac-[W(CO)3(NCMe)3] sequentially with Me2NC(=S)Cl and K[HB(pz)3] provided [W(η2-SCNMe2)(CO)2{HB(pz)3}] (11); however replacing Me2NC(=S)Cl with ClC(=S)OC6H4-Me-4 led to [WCl(CO)3{HB(pz)3}] (12).",

author = "Stephen Anderson and Cook, {Darren J.} and Hill, {Anthony F.}",

year = "2001",

month = jun,

day = "11",

doi = "10.1021/om991019h",

language = "English",

volume = "20",

pages = "2468--2476",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Metallathiirenes. 3.1 thiocarbamoyl and alkoxythiocarbonyl complexes of molybdenum(II) and tungsten(II)

AU - Anderson, Stephen

AU - Cook, Darren J.

AU - Hill, Anthony F.

PY - 2001/6/11

Y1 - 2001/6/11

N2 - Synthetic routes to thiocarbamoyl (thiocarboxamide) complexes of divalent molybdenum and tungsten are reported: The reaction of fac-[Mo(CO)3(NCMe)3] with N,N-dimethyl thiocarbamoyl chloride (Me2NC(=S)Cl) at low temperature provides a thermally labile intermediate (1) presumed on the basis of subsequent transformations to be [Mo(η2-SCNMe2)-Cl(CO)3(NCMe)]. Reactions of 1 with K[HB(pz)3] (pz = pyrazol-1-yl), NaC5H5, bipy, or tmeda provide the complexes [Mo(η2-SCNMe2)(CO)2{HB(pz)3}] (2), [Mo(η2-SCNMe2)(CO)2(η-C5 H5)] (3), [Mo(η2-SCNMe2)Cl(CO)2(bipy)] (4), and [Mo(η2-SCNMe2)Cl(CO)2(tmeda)] (5), respectively. The complex cis,cis,trans-[Mo(η2-SCNMe2)Cl(CO)2 (PPh3)2] (6) results from the oxidative addition of Me2NC(=S)Cl to [Mo(NCMe)2(CO)2(PPh3)2] and is one of two isomers obtained from the reaction of 1 with PPh3. The complex 2 may also be obtained from reaction of (i) K[Mo(CO)3{HB(pz)3}] with Me2NC(=S)Cl; (ii) [Mo(CO)3(η6-C7H8)] with Me2NC(=S)Cl and K[HB(pz)3]; and (iii) K[HB(pz)3] with either 5 or 6. Sequential treatment of either [Mo(CO)3-(NCMe)3] or [Mo(CO)3(η6-C7H8)] with ClC(=S)OR (R = C6H4Me-4, C6H5) and K[HB(pz)3] provides the complexes [Mo(η2-SCOR)(CO)2{HB(pz)3}] [R = C6H4Me-4 (7a), C6H5 (7b)]. Attempts to prepare a mononuclear thiocarbamoyl complex by addition of elemental sulfur or propene episulfide to the aminomethylidyne complex [Mo(≡CNiPr2)(CO)2{HB(pz)3}] (8) were unsuccessful; however addition of [Fe2(CO)9] to 8 provided the thermally unstable complex [MoFe(μ-CNiPr2)(CO)5{HB(pz)3}] (9), which reacts with sulfur to provide the heterobimetallic bridging thiocarbamoyl complex [MoFe(μ-SCNiPr2)(CO)5{HB(pz)3}] (10). Treating fac-[W(CO)3(NCMe)3] sequentially with Me2NC(=S)Cl and K[HB(pz)3] provided [W(η2-SCNMe2)(CO)2{HB(pz)3}] (11); however replacing Me2NC(=S)Cl with ClC(=S)OC6H4-Me-4 led to [WCl(CO)3{HB(pz)3}] (12).

AB - Synthetic routes to thiocarbamoyl (thiocarboxamide) complexes of divalent molybdenum and tungsten are reported: The reaction of fac-[Mo(CO)3(NCMe)3] with N,N-dimethyl thiocarbamoyl chloride (Me2NC(=S)Cl) at low temperature provides a thermally labile intermediate (1) presumed on the basis of subsequent transformations to be [Mo(η2-SCNMe2)-Cl(CO)3(NCMe)]. Reactions of 1 with K[HB(pz)3] (pz = pyrazol-1-yl), NaC5H5, bipy, or tmeda provide the complexes [Mo(η2-SCNMe2)(CO)2{HB(pz)3}] (2), [Mo(η2-SCNMe2)(CO)2(η-C5 H5)] (3), [Mo(η2-SCNMe2)Cl(CO)2(bipy)] (4), and [Mo(η2-SCNMe2)Cl(CO)2(tmeda)] (5), respectively. The complex cis,cis,trans-[Mo(η2-SCNMe2)Cl(CO)2 (PPh3)2] (6) results from the oxidative addition of Me2NC(=S)Cl to [Mo(NCMe)2(CO)2(PPh3)2] and is one of two isomers obtained from the reaction of 1 with PPh3. The complex 2 may also be obtained from reaction of (i) K[Mo(CO)3{HB(pz)3}] with Me2NC(=S)Cl; (ii) [Mo(CO)3(η6-C7H8)] with Me2NC(=S)Cl and K[HB(pz)3]; and (iii) K[HB(pz)3] with either 5 or 6. Sequential treatment of either [Mo(CO)3-(NCMe)3] or [Mo(CO)3(η6-C7H8)] with ClC(=S)OR (R = C6H4Me-4, C6H5) and K[HB(pz)3] provides the complexes [Mo(η2-SCOR)(CO)2{HB(pz)3}] [R = C6H4Me-4 (7a), C6H5 (7b)]. Attempts to prepare a mononuclear thiocarbamoyl complex by addition of elemental sulfur or propene episulfide to the aminomethylidyne complex [Mo(≡CNiPr2)(CO)2{HB(pz)3}] (8) were unsuccessful; however addition of [Fe2(CO)9] to 8 provided the thermally unstable complex [MoFe(μ-CNiPr2)(CO)5{HB(pz)3}] (9), which reacts with sulfur to provide the heterobimetallic bridging thiocarbamoyl complex [MoFe(μ-SCNiPr2)(CO)5{HB(pz)3}] (10). Treating fac-[W(CO)3(NCMe)3] sequentially with Me2NC(=S)Cl and K[HB(pz)3] provided [W(η2-SCNMe2)(CO)2{HB(pz)3}] (11); however replacing Me2NC(=S)Cl with ClC(=S)OC6H4-Me-4 led to [WCl(CO)3{HB(pz)3}] (12).

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U2 - 10.1021/om991019h

DO - 10.1021/om991019h

M3 - Article

SN - 0276-7333

VL - 20

SP - 2468

EP - 2476

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Metallathiirenes. 3.¹ thiocarbamoyl and alkoxythiocarbonyl complexes of molybdenum(II) and tungsten(II)

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