a10d8a7d59adacc4a7dca542a575bbbc cat_a2023m2v13n2p297.pdf fd01dbc1236f7265e98679772426e2495eb01cf1 cat_a2023m2v13n2p297.pdf 6d2f75ebed4ee35d2d272e09d46dccc7ce5f01224382d6c0fe3bb3902f56882f cat_a2023m2v13n2p297.pdf Title: Synthesis of Phenol-Tagged Ruthenium Alkylidene Olefin Metathesis Catalysts for Robust Immobilisation Inside Metal–Organic Framework Support Subject: Two new unsymmetrical N-heterocyclic carbene ligand (uNHC)-based ruthenium complexes featuring phenolic OH function were obtained and fully characterised. The more active one was then immobilised on the metal–organic framework (MOF) solid support (Al)MIL-101-NH2. The catalytic activity of such a heterogeneous system was tested, showing that, while the heterogeneous catalyst is less active than the corresponding homogeneous catalyst in solution, it can catalyse selected olefin metathesis reactions, serving as the proof-of-concept for the immobilisation of catalytically active complexes in MOFs using a phenolic tag. Keywords: olefin metathesis; ruthenium; metal–organic framework (MOF); immobilisation Author: Maryana Nadirova, Joel Cejas-Sánchez, Rosa María Sebastián, Marcin Wiszniewski, Michał J. Chmielewski, Anna Kajetanowicz and Karol Grela Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Sat Jan 28 09:59:48 2023 CET ModDate: Mon Apr 17 16:47:11 2023 CEST Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 12 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 4772468 bytes Optimized: yes PDF version: 1.7 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- CMRYXI+VnURWPalladioL Type 1 Custom yes yes no 709 0 XULWLO+URWPalladioL-Bold Type 1 Custom yes yes no 713 0 SGFHJQ+URWPalladioL-Roma Type 1 Custom yes yes no 716 0 APCLVR+URWPalladioL-Ital Type 1 Custom yes yes no 719 0 SSNIUI+VnURWPalladioL-Bold Type 1 Custom yes yes no 722 0 CGDLTM+TimesNewRomanPS-BoldItalicMT Type 1C WinAnsi yes yes no 731 0 XFIZIB+CMSY10 Type 1 Builtin yes yes no 568 0 CIDFont+F3 CID TrueType Identity-H yes no yes 229 0 CIDFont+F1 CID TrueType Identity-H yes no yes 235 0 CIDFont+F2 CID TrueType Identity-H yes no yes 241 0 CIDFont+F3 CID TrueType Identity-H yes no yes 251 0 CIDFont+F1 CID TrueType Identity-H yes no yes 257 0 CIDFont+F2 CID TrueType Identity-H yes no yes 263 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 278 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 281 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 284 0 BCDIEE+PalatinoLinotype-Roman CID TrueType Identity-H yes yes yes 289 0 ArialMT CID TrueType Identity-H yes no yes 294 0 Arial-BoldMT CID TrueType Identity-H yes no yes 299 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 305 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 308 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 311 0 BCDIEE+PalatinoLinotype-Roman CID TrueType Identity-H yes yes yes 316 0 ArialMT CID TrueType Identity-H yes no yes 321 0 Arial-BoldMT CID TrueType Identity-H yes no yes 326 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 339 0 BCDKEE+Cambria TrueType WinAnsi yes yes no 342 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 345 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 348 0 BCDIEE+PalatinoLinotype-Roman CID TrueType Identity-H yes yes yes 353 0 ASJIQB+CMBSY10 Type 1 Builtin yes yes no 609 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 364 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 367 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 370 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 375 0 BCDIEE+PalatinoLinotype-Roman CID TrueType Identity-H yes yes yes 380 0 ArialMT CID TrueType Identity-H yes no yes 385 0 Arial-BoldMT CID TrueType Identity-H yes no yes 390 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 396 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 399 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 402 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 407 0 ArialMT CID TrueType Identity-H yes no yes 412 0 Arial-BoldMT CID TrueType Identity-H yes no yes 417 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 423 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 426 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 429 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 434 0 ArialMT CID TrueType Identity-H yes no yes 439 0 Arial-BoldMT CID TrueType Identity-H yes no yes 444 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 613 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 619 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 618 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 621 0 ArialMT CID TrueType Identity-H yes no yes 582 0 Arial-BoldMT CID TrueType Identity-H yes no yes 587 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 575 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 578 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 593 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 596 0 ArialMT CID TrueType Identity-H yes no yes 592 0 Arial-BoldMT CID TrueType Identity-H yes no yes 600 0 VAJWJZ+EURM10 Type 1 Builtin yes yes no 628 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 452 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 455 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 458 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 463 0 BCDIEE+PalatinoLinotype-Roman CID TrueType Identity-H yes yes yes 468 0 ArialMT CID TrueType Identity-H yes no yes 473 0 Arial-BoldMT CID TrueType Identity-H yes no yes 478 0 BCDEEE+PalatinoLinotype-Bold TrueType WinAnsi yes yes no 484 0 BCDFEE+PalatinoLinotype-Roman TrueType WinAnsi yes yes no 487 0 BCDGEE+PalatinoLinotype-Italic TrueType WinAnsi yes yes no 490 0 BCDHEE+PalatinoLinotype-Bold CID TrueType Identity-H yes yes yes 495 0 BCDIEE+PalatinoLinotype-Roman CID TrueType Identity-H yes yes yes 500 0 ArialMT CID TrueType Identity-H yes no yes 505 0 Arial-BoldMT CID TrueType Identity-H yes no yes 510 0 Jhove (Rel. 1.22.1, 2019-04-17) Date: 2023-04-18 02:26:26 CEST RepresentationInformation: cat_a2023m2v13n2p297.pdf ReportingModule: PDF-hul, Rel. 1.12.1 (2019-04-17) LastModified: 2023-04-17 17:02:28 CEST Size: 4772468 Format: PDF Version: 1.7 Status: Well-Formed and valid SignatureMatches: PDF-hul MIMEtype: application/pdf Profile: Linearized PDF PDFMetadata: Objects: 0 FreeObjects: 1 IncrementalUpdates: 0 DocumentCatalog: PageLayout: SinglePage PageMode: UseNone Outlines: Item: Title: Introduction Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1060b431 Item: Title: Results and Discussion Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@612679d6 Item: Title: Materials and Methods Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@11758f2a Item: Title: Conclusions Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@e720b71 Item: Title: References Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1b26f7b2 Filters: FilterPipeline: FlateDecode Fonts: Type1: Font: BaseFont: ASJIQB+CMBSY10 FontSubset: true FirstChar: 1 LastChar: 1 FontDescriptor: FontName: ASJIQB+CMBSY10 Flags: Symbolic FontBBox: -26, -940, 1332, 825 FontFile: true Font: BaseFont: SSNIUI+VnURWPalladioL-Bold FontSubset: true FirstChar: 161 LastChar: 189 FontDescriptor: FontName: SSNIUI+VnURWPalladioL-Bold Flags: Symbolic FontBBox: -152, -301, 1000, 935 FontFile: true EncodingDictionary: Differences: true Font: BaseFont: VAJWJZ+EURM10 FontSubset: true FirstChar: 11 LastChar: 34 FontDescriptor: FontName: VAJWJZ+EURM10 Flags: Symbolic FontBBox: -32, -243, 1060, 720 FontFile: true Font: BaseFont: CMRYXI+VnURWPalladioL FontSubset: true FirstChar: 161 LastChar: 243 FontDescriptor: FontName: CMRYXI+VnURWPalladioL Flags: Symbolic FontBBox: -166, -283, 1021, 943 FontFile: true EncodingDictionary: Differences: true Font: BaseFont: XFIZIB+CMSY10 FontSubset: true FirstChar: 0 LastChar: 14 FontDescriptor: FontName: XFIZIB+CMSY10 Flags: Symbolic FontBBox: -29, -960, 1116, 775 FontFile: true Font: BaseFont: XULWLO+URWPalladioL-Bold FontSubset: true FirstChar: 2 LastChar: 150 FontDescriptor: FontName: XULWLO+URWPalladioL-Bold Flags: Symbolic FontBBox: -152, -301, 1000, 935 FontFile: true EncodingDictionary: Differences: true Font: BaseFont: SGFHJQ+URWPalladioL-Roma FontSubset: true FirstChar: 1 LastChar: 246 FontDescriptor: FontName: SGFHJQ+URWPalladioL-Roma Flags: Symbolic FontBBox: -166, -283, 1021, 943 FontFile: true EncodingDictionary: Differences: true Font: BaseFont: APCLVR+URWPalladioL-Ital FontSubset: true FirstChar: 2 LastChar: 151 FontDescriptor: FontName: APCLVR+URWPalladioL-Ital Flags: Symbolic FontBBox: -170, -305, 1010, 941 FontFile: true EncodingDictionary: Differences: true XMP: application/pdf Maryana Nadirova, Joel Cejas-Sánchez, Rosa María Sebastián, Marcin Wiszniewski, Michał J. Chmielewski, Anna Kajetanowicz and Karol Grela Two new unsymmetrical N-heterocyclic carbene ligand (uNHC)-based ruthenium complexes featuring phenolic OH function were obtained and fully characterised. The more active one was then immobilised on the metal–organic framework (MOF) solid support (Al)MIL-101-NH2. The catalytic activity of such a heterogeneous system was tested, showing that, while the heterogeneous catalyst is less active than the corresponding homogeneous catalyst in solution, it can catalyse selected olefin metathesis reactions, serving as the proof-of-concept for the immobilisation of catalytically active complexes in MOFs using a phenolic tag. Synthesis of Phenol-Tagged Ruthenium Alkylidene Olefin Metathesis Catalysts for Robust Immobilisation Inside Metal–Organic Framework Support 2023-01-28T16:59:48+08:00 LaTeX with hyperref 2023-04-17T16:47:11+02:00 2023-04-17T16:47:11+02:00 olefin metathesis; ruthenium; metal–organic framework (MOF); immobilisation pdfTeX-1.40.21 uuid:811655fb-4e4f-43e9-961e-2af1f82b5234 uuid:3f831d53-a93b-47db-b921-92a3df688e71 Pages: Page: Sequence: 1 Annotations: Annotation: Subtype: Link Rect: 34, 293, 152, 302 Annotation: Subtype: Link Rect: 34, 283, 78, 290 Annotation: Subtype: Link Rect: 34, 164, 96, 186 Annotation: Subtype: Link Rect: 126, 90, 154, 99 Annotation: Subtype: Link Rect: 34, 78, 147, 87 Annotation: Subtype: Link Rect: 34, 756, 163, 792 Annotation: Subtype: Link Rect: 515, 756, 560, 792 Annotation: Subtype: Link Rect: 231, 642, 242, 655 Annotation: Subtype: Link Rect: 350, 642, 361, 655 Annotation: Subtype: Link Rect: 465, 642, 476, 655 Annotation: Subtype: Link Rect: 152, 629, 163, 643 Annotation: Subtype: Link Rect: 269, 629, 280, 643 Annotation: Subtype: Link Rect: 362, 338, 369, 347 ActionDest: 148 Annotation: Subtype: Link Rect: 370, 338, 377, 347 ActionDest: 148 Annotation: Subtype: Link Rect: 549, 263, 556, 272 ActionDest: 148 Annotation: Subtype: Link Rect: 298, 187, 305, 197 ActionDest: 148 Annotation: Subtype: Link Rect: 308, 187, 315, 197 ActionDest: 148 Annotation: Subtype: Link Rect: 548, 137, 555, 146 ActionDest: 151 Annotation: Subtype: Link Rect: 411, 125, 418, 134 ActionDest: 151 Annotation: Subtype: Link Rect: 421, 125, 433, 134 ActionDest: 151 Annotation: Subtype: Link Rect: 114, 17, 255, 28 Annotation: Subtype: Link Rect: 406, 17, 560, 28 Annotation: Subtype: Link Rect: 34, 414, 87, 433 Page: Sequence: 2 Annotations: Annotation: Subtype: Link Rect: 522, 660, 529, 669 ActionDest: 151 Annotation: Subtype: Link Rect: 530, 660, 542, 669 ActionDest: 151 Annotation: Subtype: Link Rect: 544, 560, 556, 569 ActionDest: 151 Annotation: Subtype: Link Rect: 202, 472, 214, 481 ActionDest: 151 Annotation: Subtype: Link Rect: 464, 447, 476, 456 ActionDest: 151 Annotation: Subtype: Link Rect: 459, 422, 471, 431 ActionDest: 151 Annotation: Subtype: Link Rect: 240, 384, 251, 393 ActionDest: 151 Annotation: Subtype: Link Rect: 499, 359, 511, 368 ActionDest: 151 Annotation: Subtype: Link Rect: 302, 283, 314, 293 ActionDest: 151 Annotation: Subtype: Link Rect: 400, 283, 412, 293 ActionDest: 151 Annotation: Subtype: Link Rect: 481, 283, 493, 293 ActionDest: 151 Annotation: Subtype: Link Rect: 496, 283, 508, 293 ActionDest: 151 Annotation: Subtype: Link Rect: 238, 271, 250, 280 ActionDest: 151 Annotation: Subtype: Link Rect: 251, 271, 263, 280 ActionDest: 151 Annotation: Subtype: Link Rect: 420, 233, 432, 242 ActionDest: 151 Annotation: Subtype: Link Rect: 403, 133, 415, 142 ActionDest: 151 Annotation: Subtype: Link Rect: 416, 133, 428, 142 ActionDest: 151 Annotation: Subtype: Link Rect: 487, 118, 494, 130 ActionDest: 4 Page: Sequence: 3 Annotations: Annotation: Subtype: Link Rect: 431, 309, 438, 321 ActionDest: 16 Annotation: Subtype: Link Rect: 445, 311, 457, 321 ActionDest: 151 Annotation: Subtype: Link Rect: 436, 208, 443, 220 ActionDest: 16 Annotation: Subtype: Link Rect: 423, 136, 434, 145 ActionDest: 151 Annotation: Subtype: Link Rect: 275, 60, 287, 69 ActionDest: 154 Annotation: Subtype: Link Rect: 287, 60, 299, 69 ActionDest: 154 Page: Sequence: 4 Annotations: Annotation: Subtype: Link Rect: 468, 142, 475, 154 ActionDest: 28 Annotation: Subtype: Link Rect: 515, 132, 527, 142 ActionDest: 154 Page: Sequence: 5 Annotations: Annotation: Subtype: Link Rect: 193, 698, 204, 707 ActionDest: 154 Annotation: Subtype: Link Rect: 205, 698, 217, 707 ActionDest: 154 Annotation: Subtype: Link Rect: 182, 673, 194, 682 ActionDest: 151 Annotation: Subtype: Link Rect: 195, 673, 207, 682 ActionDest: 154 Annotation: Subtype: Link Rect: 207, 673, 219, 682 ActionDest: 154 Annotation: Subtype: Link Rect: 222, 673, 234, 682 ActionDest: 154 Annotation: Subtype: Link Rect: 505, 657, 512, 669 ActionDest: 28 Page: Sequence: 6 Annotations: Annotation: Subtype: Link Rect: 544, 660, 556, 669 ActionDest: 154 Annotation: Subtype: Link Rect: 544, 610, 556, 619 ActionDest: 151 Annotation: Subtype: Link Rect: 552, 595, 559, 607 ActionDest: 63 Annotation: Subtype: Link Rect: 512, 469, 519, 481 ActionDest: 63 Annotation: Subtype: Link Rect: 444, 92, 451, 104 ActionDest: 74 Page: Sequence: 7 Annotations: Annotation: Subtype: Link Rect: 466, 733, 473, 745 ActionDest: 28 Annotation: Subtype: Link Rect: 407, 392, 419, 400 ActionDest: 151 Annotation: Subtype: Link Rect: 266, 326, 273, 338 ActionDest: 74 Page: Sequence: 8 Page: Sequence: 9 Annotations: Annotation: Subtype: Link Rect: 333, 698, 345, 707 ActionDest: 154 Annotation: Subtype: Link Rect: 429, 698, 441, 707 ActionDest: 154 Page: Sequence: 10 Annotations: Annotation: Subtype: Link Rect: 536, 609, 560, 620 Annotation: Subtype: Link Rect: 165, 597, 383, 609 Annotation: Subtype: Link Rect: 376, 407, 387, 415 ActionDest: 154 Annotation: Subtype: Link Rect: 387, 406, 398, 415 ActionDest: 154 Annotation: Subtype: Link Rect: 140, 126, 177, 136 Annotation: Subtype: Link Rect: 184, 126, 220, 136 Annotation: Subtype: Link Rect: 104, 103, 142, 113 Annotation: Subtype: Link Rect: 148, 103, 184, 113 Annotation: Subtype: Link Rect: 267, 79, 304, 90 Page: Sequence: 11 Annotations: Annotation: Subtype: Link Rect: 59, 699, 96, 710 Annotation: Subtype: Link Rect: 113, 676, 150, 687 Annotation: Subtype: Link Rect: 410, 652, 447, 664 Annotation: Subtype: Link Rect: 113, 630, 151, 640 Annotation: Subtype: Link Rect: 59, 596, 96, 606 Annotation: Subtype: Link Rect: 321, 572, 358, 583 Annotation: Subtype: Link Rect: 90, 538, 128, 548 Annotation: Subtype: Link Rect: 351, 514, 388, 525 Annotation: Subtype: Link Rect: 294, 480, 332, 491 Annotation: Subtype: Link Rect: 328, 457, 365, 468 Annotation: Subtype: Link Rect: 240, 434, 277, 445 Annotation: Subtype: Link Rect: 104, 400, 141, 410 Annotation: Subtype: Link Rect: 371, 376, 408, 387 Annotation: Subtype: Link Rect: 414, 376, 450, 387 Annotation: Subtype: Link Rect: 363, 353, 401, 364 Annotation: Subtype: Link Rect: 406, 330, 444, 341 Annotation: Subtype: Link Rect: 215, 297, 253, 307 Annotation: Subtype: Link Rect: 246, 261, 284, 272 Annotation: Subtype: Link Rect: 385, 238, 423, 249 Annotation: Subtype: Link Rect: 429, 238, 465, 249 Annotation: Subtype: Link Rect: 179, 205, 217, 215 Annotation: Subtype: Link Rect: 204, 170, 242, 180 Annotation: Subtype: Link Rect: 394, 146, 431, 157 Annotation: Subtype: Link Rect: 437, 146, 473, 157 Annotation: Subtype: Link Rect: 227, 123, 264, 134 Annotation: Subtype: Link Rect: 402, 100, 440, 111 Annotation: Subtype: Link Rect: 364, 77, 401, 88 Page: Sequence: 12 Annotations: Annotation: Subtype: Link Rect: 104, 711, 142, 721 Annotation: Subtype: Link Rect: 95, 676, 133, 687 Annotation: Subtype: Link Rect: 501, 652, 539, 664 Annotation: Subtype: Link Rect: 59, 619, 96, 629 Annotation: Subtype: Link Rect: 202, 584, 239, 594 Annotation: Subtype: Link Rect: 245, 584, 281, 594 Annotation: Subtype: Link Rect: 425, 549, 463, 560 Annotation: Subtype: Link Rect: 469, 549, 505, 560 Annotation: Subtype: Link Rect: 59, 515, 96, 525 Annotation: Subtype: Link Rect: 206, 481, 244, 491 Annotation: Subtype: Link Rect: 392, 457, 430, 468 Annotation: Subtype: Link Rect: 104, 435, 141, 445 Annotation: Subtype: Link Rect: 269, 411, 306, 422 Annotation: Subtype: Link Rect: 348, 388, 385, 399 Annotation: Subtype: Link Rect: 520, 376, 557, 387 Checksum: 999ec0cd Type: CRC32 Checksum: a10d8a7d59adacc4a7dca542a575bbbc Type: MD5 Checksum: fd01dbc1236f7265e98679772426e2495eb01cf1 Type: SHA-1