1. A compound of formula I, or II, or III:
wherein:
M is molybdenum or tungsten;
R1 is optionally substituted
each of R2 and R3 is independently R, \u2014OR, \u2014SR, \u2014N(R)2, \u2014OC(O)R, \u2014SOR, \u2014SO2R, \u2014SO2N(R)2, \u2014C(O)N(R)2, \u2014NRC(O)R, or \u2014NRSO2R;
R2\u2032 and R3\u2032 are taken together with M to form an optionally substituted 3-8 membered saturated or partially unsaturated ring having, in addition to M, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each of R4 and R5 is independently halogen, R, \u2014N(R)2, \u2014NRC(O)R, \u2014NRC(O)OR, \u2014NRC(O)N(R)2, \u2014NRSO2R, \u2014NRSO2N(R)2, \u2014NROR, \u2014OR, \u2014OSi(R)3, \u2014OAra, or an optionally substituted group selected from a 5-6 membered monocyclic heteroaryl ring having at least one nitrogen and 0-3 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having at least one nitrogen and 0-2 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having at least one nitrogen and 0-4 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having at least one nitrogen and 0-4 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur;
Ara is
m is 0-3;
Ring B is an optionally substituted group selected from phenyl or a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
p is 1-5;
q is 0-5;
t is 0-4;
each of Ring B\u2032, Ring C and Ring D is independently an optionally substituted group selected from phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-14 membered bicyclic or tricyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
each R7 is independently halogen, R, \u2014CN, \u2014NO2, \u2014OR, \u2014SR, \u2014S(O)R, \u2014S(O)2R, \u2014OSi(R)3, \u2014N(R)2, \u2014NRC(O)R, \u2014NRC(O)OR, \u2014NRC(O)N(R)2, \u2014NRSO2R, \u2014NRSO2N(R)2, or \u2014NROR;
each of Rx, Ry and Rz is independently an electron-withdrawing group;
each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or:
two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
n is 0-2; and
each R6 is independently a neutral ligand.
2. The compound of claim 1, wherein the compound is a compound of formula I, and one of R2 and R3 is hydrogen and the other is optionally substituted C1-20 aliphatic.
3. The compound of claim 1, wherein the compound is a compound of formula II, and R2\u2032 and R3\u2032 are taken together with M to form an optionally substituted 3-membered ring.
4. The compound of claim 1, wherein the compound is a compound of formula I or II, and each of R4 and R5 is independently \u2014OR, \u2014OSi(R)3, or \u2014OAra.
5. The compound of claim 4, wherein each of R4 and R5 is \u2014OR, wherein R is optionally substituted phenyl.
6. The compound of claim 4, wherein each of R4 and R5 is triflate, \u2014O-2,6-(CHPh2)2-4-MeC6H2, DFTO, \u2014OC(CF3)3 or \u2014OC(C6F5)3.
7. The compound of claim 4, wherein M is tungsten.
8. The compound of claim 7, wherein R1 is
9. The compound of claim 1, wherein the compound is a compound of formula III, and each of R4 and R5 is independently \u2014Cl.
10. The compound of claim 9, wherein M is tungsten.
11. The compound of claim 1, wherein n is 1.
12. The compound of claim 11, wherein R6 is a bidentate ligand, and R6 is 1,2-dimethoxyethane (DME).
13. The compound of claim 1, wherein n is 0.
14. The compound of claim 1, wherein the compound is selected from:
W(NArCl3)(CHCMe3)(OTf)2(DME), W(NArCl3)(CHCMe3)(2,5-Me2Pyr)2, W(NArBr3)(CHCMe3)(OTf)2(DME), W(NArCl2CF3)2(CHCMe3)(OTf)2(DME), W(NAr(CF3)2)(CHCMe3)(OTf)2(DME), Mo(NC6F5)(CHCMe2Ph)(OTf)2(DME), Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2, Mo(NC6F5)(CHCMe2Ph)OC(CF3)32, Mo(NC6F5)(CHCMe2Ph)OC(C6F5)32, Mo(NC6F5)(CHCMe2Ph)(ODFT)2, W(NC6F5)(CH-t-Bu)(DME)(OTf)2, W(NC6F5)(CH-t-Bu)(THF)2(OTf)2, W(NC6F5)(CH-t-Bu)(DME)(THF)(OTf)2, W(NC6F5)(CH-t-Bu)(\u03bc-DME)(OTf)2x, W(NC6F5)(CH-t-Bu)(DME)(Pyr)2, W(NC6F5)(CH-t-Bu)(DME)OC(CF3)32, W(NC6F5)(CH-t-Bu)OC(C6F5)32, W(NC6F5)(CH-t-Bu)(ODFT)2, Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(HMTO), W(NC6F5)(CH-t-Bu)(dme)1.5(Pyr)2, W(NC6F5)(CHCMe2Ph)(Me2Pyr)(HMTO), W(NArCl3)(CH-t-Bu)(Pyr)(DFTO), W(NArCl3)(CH-t-Bu)(Pyr)(HMTO), W(NArCl3)(CH-t-Bu)(Pyr)(HIPTO), W(NArBr3)(CH-t-Bu)(Pyr)(DFTO), W(NArBr3)(CH-t-Bu)(Pyr)(HMTO), W(NArBr3)(CH-t-Bu)(Pyr)(HIPTO), W(NArCl2CF3)(CH-t-Bu)(Pyr)(DFTO), W(NArCl2CF3)(CH-t-Bu)(Pyr)(HMTO), W(NArCl2CF3)(CH-t-Bu)(Pyr)(HIPTO), W(NAr(CF3)2)(CH-t-Bu)(Pyr)(DFTO), W(NAr(CF3)2)(CH-t-Bu)(Pyr)(HMTO), W(NAr(CF3)2)(CH-t-Bu)(Pyr)(HIPTO), W(NArCl3)(CH-t-Bu)(ORF6), W(NArCl3)(CH-t-Bu)(ORF9), W(NArBr3)(CH-t-Bu)(ORF6), W(NArBr3)(CH-t-Bu)(ORF9), W(NArCl2CF3)(CH-t-Bu)(ORF6), W(NArCl2CF3)(CH-t-Bu)(ORF9), W(NAr(CF3)2)(CH-t-Bu)(ORF6), W(NAr(CF3)2)(CH-t-Bu)(ORF9), W(NArCl3)(CHCMe3)(Me2Pyr)(OHMT), W(NArCl3)(CHCMe3)(Me2pyr)(ODFT), W(NArCl3)(CHCMe3)(Me2pyr)(OTript), W(NArCl3)(CHCMe3)(ODBMP)2, W(NArBr3)(CHCMe3)(ODBMP)2, W(NArCl2CF3)(CHCMe3)(ODBMP)2, W(NAr(CF3)2)(CHCMe3)(ODBMP)2, W(NAr(CF3)2)(CHCMe3)(ODBMP)2.2DME, W(NArCl)(CHCMe3)(OTf)2(dme), W(NArCl)(CHCMe3)(ODBMP)2, W(NArF)(CHCMe3)(OTf)2(dme), W(NArF)(CHCMe3)(ODBMP)2, W(NAr\u2032)(CHCMe3)(OTf)2(dme), W(NAr\u2032)(CHCMe3)(ODBMP)2, W(NAr\u2033)(CHCMe2Ph)(OTf)2(dme), W(NAr\u2033)(CHCMe2Ph)(ODBMP)2, W(NC6F5)(CH2CH2CH2)OC(CF3)32, Mo(NC6F5)2Cl2(DME), W(NC6F5)2Cl2(DME), Mo(NC6F5)2(CH2CMe2Ph)2, Mo(NC6F5)2(CH2CMe2Ph)2(Et2O), W(NC6F5)2(CH2CMe3)2, W(NArCl3)2Cl2(DME), W(NArCl3)2(CH2CMe3)2, W(NArBr3)2Cl2(DME), W(NArBr3)2(CH2CMe3)2, W(NArCl2CF3)2Cl2(DME), W(NArCl2CF3)2(CHCMe3)2, W(NAr(CF3)2)2Cl2(DME), and W(NAr(CF3)2)2(CH2CMe3)2,
wherein ArCl3 is 2,4,6-trichlorophenyl, ArBr3 is 2,4,6-tribromophenyl, ArCl2CF3 is 2,6-dichloro-4-(trifluoromethyl)phenyl, Ar(CF3)2 is 3,5-bis(trifluoromethyl)phenyl, ORF6 is hexafluoro-tert-butoxide (\u2014OCMe(CF3)2), ORF9 is perfluoro-tert-butoxide (\u2014OC(CF3)3), Ar\u2032 is 2,6-Me2C6H3, and Ar\u2033 is 3,5-Me2C6H3.
15. A compound having the structure of:
or HO-2,6-(CHPh2)2-4-MeC6H2,
or a salt thereof.
16. A method for preparing a compound of claim 1, comprising steps of:
1) providing a first compound having the structure of formula IV:
2) reacting the first compound with a compound having the structure of R1NSO.
17. A method for preparing a compound of claim 1, comprising providing a first compound having the structure of formula R1N(R)Si(R)3.
18. The method of claim 17, further comprising providing a compound having the structure of M(R4)6.
19. The method of claim 18, wherein M(R4)6 is WCl6.
20. A method for performing a metathesis reaction, comprising providing a compound of formula I.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A grass-cutting head with an axis of rotation, the grass-cutting head comprising:
a body forming a housing for at least one spool of cutting line, provided with at least one outlet hole for an end of said cutting line wound on said spool, said body comprising a projection and a substantially cylindrical surface, said projection having a shape of a portion of a spiral, said projection gradually projecting from said substantially cylindrical surface of said body, said projection ending with an end surface, said end surface intersecting said substantially cylindrical surface, said outlet hole being arranged on said end surface;
a guide channel in communication with said at least one outlet hole for receiving the cutting line, said guide channel extending from the inside of said housing towards the outlet hole and having an inclined shape, gradually moving away from said axis of rotation, said guide channel being provided in said projection, said guide channel defining a radially outward concave guiding surface formed in said body, said concave guiding surface having a concavity facing the axis of rotation, wherein a portion of said cutting line inside said guide channel has a concave path in an operating phase and a non-operating phase, said concave path being the same in said operating phase and in said non-operating phase.
2. Grass-cutting head as claimed in claim 1, wherein said outlet hole is on a surface inclined by an angle differing from 90\xb0 with respect to a radial plane containing the axis of rotation and passing through the center of the hole.
3. Grass-cutting head as claimed in claim 2, wherein the outlet hole defines a direction of projection of the line from the body of the head which is not radial and inclined by an angle between 30\xb0 and 90\xb0 with respect to a radial direction.
4. A grass-cutting head as claimed in claim 2, wherein the outlet hole defines a direction of projection of the line from the body of the head which is not radial and inclined by an angle between 60\xb0 and 90\xb0 with respect to a radial direction.
5. Grass-cutting head as claimed in claim 1, wherein said guide channel has an approximately spiral shape, said at least one projection spanning substantially half of a circumference of said body.
6. Grass-cutting head as claimed in claim 5, wherein the surface on which the outlet hole is located forms with a radial plane an angle between 0\xb0 and 80\xb0.
7. Grass-cutting head as claimed in claim 5, wherein the surface on which the outlet hole is located has a substantially radial extension with respect to the axis of rotation of the head.
8. Grass-cutting head as claimed in claim 5, wherein the surface on which the outlet hole is located forms with a radial plane an angle between 0\xb0 and 45\xb0.
9. Grass-cutting head as claimed in claim 5, wherein the surface on which the outlet hole is located forms with a radial plane an angle between 0\xb0 and 30\xb0.
10. Grass-cutting head as claimed in claim 1, wherein the outlet hole defines a direction of projection of the line from the body of the head which is not radial and inclined by an angle between 30\xb0 and 90\xb0 with respect to a radial direction.
11. Grass-cutting head as claimed in claim 1, wherein the outlet hole defines a direction of projection of the line from the body of the head which is not radial and inclined by an angle between 60\xb0 and 90\xb0 with respect to a radial direction.
12. A grass-cutting head as claimed in claim 1, wherein a portion of said cutting line extends from the inside of said housing through said guide channel and said at least one outlet hole to a position located outside of said projection.
13. Grass-cutting head as claimed in claim 1, wherein said projection is made integral with said body, with the same material of which said body is formed or with a different material.
14. A grass-cutting head, the grass-cutting head comprising:
a spool of cutting line;
a grass-cutting head body forming a housing for said spool of cutting line, said body being movable about an axis of rotation, said body comprising a cylindrical outer surface and a side surface formed by a series of spiral portions arranged one after another, said spiral portions being defined by at least two projections extending from said cylindrical outer surface, each of said projections comprising an inner projection surface, each of said at least two projections having a first end and a second end, wherein a thickness of said at least projection increases from said first end to said second end, each of said at least projections extending in a circumferential direction of said body, each of said at least one projections having an end surface located at said second end, said end surface comprising an outlet hole, said inner projection surface defining at least a portion of a guide channel extending from an interior portion of said housing to said outlet hole, said outlet hole being in communication with said guide channel, wherein a portion of said cutting line extends from the interior portion of said housing through said guide channel and said at least one outlet hole to a position located outside of said body and said at least one projection
wherein one end of said guide channel is located at a first distance from said axis of rotation, another end of said guide channel being located at a second distance from the axis of rotation, said another end of said guide channel being adjacent to said end surface, said second distance being greater than said first distance, wherein each of said at least two projections spans substantially half of a circumference of said body.
15. A grass-cutting head in accordance with claim 14, wherein said channel extends in an inclined direction, said channel having an inclined shape, said thickness of said at least one projection at said first end being less than said thickness of said at least one projection at said second end.
16. A grass-cutting head in accordance with claim 15, wherein said at least one projection has a shape of a portion of a spiral.
17. A grass-cutting head in accordance with claim 16, wherein said end surface intersects said substantially cylindrical surface.
18. A grass-cutting head, the grass-cutting head comprising:
a spool of cutting line;
a grass-cutting head housing comprising a recess, said recess receiving said spool of cutting line, said grass-cutting head housing being movable about an axis of rotation, said grass-cutting head housing comprising an outer surface defining at least a substantially cylindrical outer wall portion and at least one projection, said at least one projection comprising an inner projection surface and an outer projection surface, said outer projection surface and said inner projection surface extending about said axis of rotation, said at least one projection having a first end and a second end, said first end being adjacent to one portion of said substantially cylindrical outer wall portion, said second end being adjacent to another portion of said substantially cylindrical outer wall portion, said at least one projection having a thickness extending in a radial direction from said substantially cylindrical outer wall portion, wherein said thickness of said at least one projection increases from said first end to said second end in a circumferential direction of said grass-cutting head, said outer projection surface extending from said first end to said second end in said circumferential direction to define an outer circumferential portion of said body, said at least one projection having an end surface located at said second end, said end surface defining at least a portion of an outlet hole, said inner projection surface defining at least a portion of a guide channel extending from a position at or adjacent to said recess to said outlet hole, said outlet hole being in communication with said guide channel, wherein a portion of said cutting line extends from the interior portion of said housing through said guide channel and said at least one outlet hole to a position located outside of said at least one projection, said portion of said cutting line extending in said circumferential direction in a rotating state of said grass cutting head, said portion of said cutting line extending in said circumferential direction in a non-rotating state of said grass cutting head
wherein one end of said guide channel is located at a first distance from said axis of rotation, another end of said guide channel being located at a second distance from the axis of rotation, said another end of said guide channel being adjacent to said end surface, said second distance being greater than said first distance, wherein each of said at least one projection spans substantially half of a circumference of said body.
19. A grass-cutting head in accordance with claim 18, wherein said channel extends in an inclined direction such that said channel has an inclined shape, said thickness of said at least one projection at said first end being less than said thickness of said at least one projection at said second end.
20. A grass-cutting head in accordance with claim 19, wherein said at least one projection has a shape of a portion of a spiral.
21. A grass-cutting head in accordance with claim 20, wherein said end surface is substantially perpendicular to said substantially cylindrical outer wall portion.